CORROSION

RESISTANCE OF
NICKEL AND NICKEL-
CONTAINING ALLOYS
IN CAUSTIC SODA
AND OTHER ALKALIES
(CEB-2)
A PRACTICAL GUIDE TO THE USE
OF NICKEL-CONTAINING ALLOYS
NO 281

Distributed by
Produced by NICKEL
INCO INSTITUTE
CORROSION RESISTANCE OF NICKEL
AND NICKEL-CONTAINING ALLOYS IN
CAUSTIC SODA AND OTHER ALKALIES
(CEB-2)

A PRACTICAL GUIDE TO THE USE

OF NICKEL-CONTAINING ALLOYS
NO 281

Originally, this handbook was published in 1973 by INCO,

The International Nickel Company, Inc. Today this company is part
of Vale S.A.
The Nickel Institute republished the handbook in 2020. Despite the
age of this publication the information herein is considered to be
generally valid.
Material presented in the handbook has been prepared for the
general information of the reader and should not be used or relied
on for specific applications without first securing competent advice.
The Nickel Institute, the American Iron and Steel Institute, their
members, staff and consultants do not represent or warrant its
suitability for any general or specific use and assume no liability or
responsibility of any kind in connection with the information herein.

Nickel Institute
communications@nickelinstitute.org
www.nickelinstitute.org
 Table of Contents
Page
PART I. INTRODUCTION 3

PART II. CORROSION BY CAUSTIC SODA........................... 4

A. Nickel .................................... _. . . . . . . . . . . . . . . . . 4
1. Effect of Concentration, Temperature and Carbon Content ...... _ . . . . . . 4
2. Effect of Velocity ............... _ ... __ ..................... _ 6
3. Effect of Aeration .•......................................... 6
4. Effect of System Thermal Gradients .............................. 7
5. Effect of Impurities .,. _................. _ ............ _ . . . . . . . 7
6. Effect of Stress ............................................. 8
7. Effect of Dissimilar Metal Contact .. _ ...... _ ...... _ ............. '. 8
8. Cathodic Protection. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
B. Nickel-Chromium Alloys (Alloy 600) .. _ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
C. Nickel·Copper Alloys (Alloy 400, Alloy K-500) ....................... _. 10
D. Copper-Nickel Alloys .... _ ...... _............. ___ ............ _., 11
Copper-Nickel Alloy CA 706 (90-10)
Copper-Nickel Alloy CA 710 (80-20)
Copper-Nickel Alloy CA 715 (70-30)
E. Iron-Nickel-Chromium Alloys (Alloy BOO) ......... _ .............. _ . .. 13
f. Austenitic Chromium-Nickel Stainless Steels (AISI 300 Series) . . . . . . . . . . .. 13
G. Iron-Base Nickel·Chromium...copper-MoJybdenum AHoys and Nickel-Base Chro-
mium...copper-Molybdenum Alloys .......... _ ....... __ ............. , 15
{Alloy 825. CARPENTER 20Cb-3, HASTELlOY alloy G and cast ACt CN-7M alloys}
H. Nickel-Base Molybdenum or Molybdenum·Chromium-lron Alloys. . . . . . . . . . . 16
(HASTElLOY alloy C-276, Alloy 625. HASTEllOY alloy B)
I. Cast Irons and Ni-Resists .... _ . _ .... __ .. __ . __ . . . . . . . . . . . . . . . . . . . . 17

PART m. CORROSON BY OTHER ALKAliES.. ............... .... .... 19

A. Caustic Potash (KOH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 19
B. Ammonia and Ammonium Hydroxide ............................... 20
C. Other Alkaline Solutions of Sodium and Potassium Salts ................ 22

PART IV. INDUSTRIAL APPLICATIONS. ... .... . ............... ...... 24

A. Caustic Soda Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 24
B. Caustic Potash Manufacture ..................................... 28
C. Caustic Soda Storage and Transportation .......................... ". 28
D. Soap Manufacture ....................... _ ......... _ . . . . . . . . . .. 30
E. Pulp and Paper Industry ...... __ ............... _ .. _ . . . . . . . . . . . ... 32
1_ Digesters _............................................ ... 32
2. liquor Heaters ............................................. 33
3. Black liquor Evaporators .................. _ . . . . . . . . . . . . . . . 34
4. Recausticizing ............................................. 34
f. Aluminum Industry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 35
G. Caustic fusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 35
H. Petroleum Refining ............ _.............. _ . _ . . . . . . . . . . . . .. 36
I. Caustic DescaJing . _. _.................... _ . . . . . . . . . . . . . . . . 37
J_ Reclaiming Caustic for Economy and Pollution Control. . . . . . . . . . . . . . 37

PART V. WELDING ............. __ ..... _. . . . . . . . . . . . . . . . . . . . . . 38

A. fabrication of Nickel·Clad Equipment .. _ ..................... " 38.
B. Repair of Equipment in Caustic Service ......... _ ...... _ . . . . . . . . . . .. 39
References .......... _ ......................................... ' 40
Trademarks ..................................... . . ... Inside back cover
 Table I

Nominal Compositions of Nickel Alloys in Use or Corrosion Tested in Caustic Solutions

Composition. %

M;aterial Hi Fe Cr Mo Cu C Si Mn Otber

WROUGHT MATERIALS
Nickel
Hickel 200
Hickel20t
99.5
99.5
0.15
0.15
-- -
-
0.05
0.05
0.06
0.01
0.05
0.05
0.25
0.20
-
-
DURAH.CKEL· alloy 30t 94.0 0.15 - - 0.15 0.55 0.25 0.25 AI 4.5; Ii 0.5
Nickel-Chromium Alloys
.HCOHEL· alloy 600 16.0 7.2 15.8 - 0.10 0.04 0.20 0.20 -
H.MONtC· alloy 75 71.4 0.5 20.5 - - 0.10 - - Ii 0.l5; AI 0.15
Nickel-Copper Alloys

-- -- -
MONU· alloy 400 66.0 1.35 ll.5 0.12 0.15 0.90
MON£!.,• al'lI1 K.SO!!:. 65.0 leO 29.5 0.15 0.15 0.60 AI 2.8: Ti 0.5
Copper-NiCkel Alloys
- - -
--
Copper-Nkke:1 allo, CA 706 10.0 1.25 88.0 0.3 Pb 0.05 max; In 1.0 rna.
Copper·Nickel alloy CA 710 20.0 0.75 - 78.0 - - 0.4 Pb 0.05 rna.; Zn 1.0 max
Coppef·Nlekel alloy cA 715
Iron·Nickel-Chromium Alloys
30.0 0.55 - - 61.0 - - 0.5 Pb 0.05 max; In 1.0 max

'NCOLO"- alloy 800' 32.0 46.0 20.5 - 0.30 O.M 0.35 0.75 -
Stainless Steels
AISI Type :202 5.0 67.0 18.0 - - 0.15ma. 1.0 max 8.1 N 0.25 max
AISI Type 31)2
AI5ITy,•. 304
9.0
9.5
70.5
70.0
18.0
18.0
-
-
-
-
0.15 max
0J)8 max
0.5
0.5
1.5
1.5
-
--
AISI TYlle 304l 10.0 69.0 18.0 -2.0mi.. - 0.03 max 0.5 1.3
-- ---
AISI tYPe 316 13.0 65.0 17.0 O.OS max 0.5 1.7
AISI tJllO 316l 13.0 65.0 17.0 2.0 min 0.03 max 0.5 1.8
AISI Type 309 13.5 60.5 23.0 - -- 0.20 malt 1.0 max 2.0m3X
AISI Type 310
AISI Type 330
20.0
35.0
52.0
41.0
25.0
1.5.1)
-- -
0.25mn
0.25 rna.
1.0 max
1.0 rna.
2.0ma.
2.0 mal
-
-
AISI Type 347 11.0 68.0 18.0 - - 0.08mu 1.0 max 2.0mu Cb;- Ta IOxC min
AISI Type. 438 - Bal 17.0 - - 0.12 max - - -
Iron Base Nicket·Chromium-Copper-MoIybxlenum Alloys
c;"'Rn'n:~- Stainless No. 20 <1'
CARPEfC-r£R' Sta,"t~$s No. 2OCb-3
29.0
34.0
43.0
39.0
20.0
20.0
2.0 min
2.5
3.0m;n
3.3
0.07 max
0.01 max
1.0
0.6
0.8
08 Cb+Ta 0.6
-
Nickel Ba';'e l'bn-Chromium·MoIybdenum Anoys
'HCOl.OY- a!Joy 825 41.8 30.0 21.5 3.0 1.8 0.03 0.35 0.65 AI 0.15: Ii 0.9
HAST£LLO.. " alloy G 45.0 19.5 22.2 6.5 2.0 0.03 0.35 1.3 W 0.5; Cn ,. Ta 2.12
HAST£t..~OY· :alloy C ~2) ~.O 5.0 15.5 16.0 - 0.08 max 1.0 rna. 1.0 max Co 2.5ma<;
W 4.0: V 0.4 max
HASTELLO.. - alloy C·2l6 54.0 5.0 15.5 16.0 - 0.02 max 0.05max 1.0max Co 2.5 rna.;
W 4.0: V OA max
'HC_I:L - alloy 625 60.0 5.0ma. 21.5 9.0 - 0.10 max 0.5 max 0.5 max Cb- Ta 3.65
Nickel Base Molybdenum Alioy
..ASULLO'\'- alloy B 61.0 5.0 1.0 max 28.0 - 0.05 max - - Co 2.5 rna.: V 0.2·0A;
P 0.025 rna.;
S 0.030 max

CAST MATERIALS
Nickel
America.. Casti"e Institute
ACI CZ·l00 95.0 min 1.5 max - - - 1.0 max 2.. 0 1.5 max -
Nickel·Ch.romlum·fron Alloy
ACI CY·40 70.0 9.5 15.5 - - 0.3 3.0 max 1.5 max -
Nickel-Copper Alloys
Hickel·Copper alloy 50S 64.0 2.0 - - 29.0 O.OS 4.0 0.80 -
ACI "'-35
Stainless Steels
64.0 3.5 max - - 29.5 (1.35 mall 2:.0 mat 1.5 max -
ACI Cr-8
ACI Cf·8M
19.5
19.5
66.0
63.0
9.5
10.5
-2.5 -- 0.08mllll:
OJl8 max
2.0m,n
1.5ma.
1.5 mall
1.5 max
-
-
ACI CA·tS
ACt HA -
1.0 max 83.0
87.0
12.8
9.0
Q.5max
1.1 --
0.ISm3l
0,20mu'
1.5mu
).0 rna.
1.0ma.
O.S
--
Iron Base Nickel-ChromiUm-CjPper Alloys I
--
wo......tn:· Stainless 24.0 48.0 20.0 3.0 1.75 0.1)7 max 3.3 0.6
ACI CN-7M "'0 29.0 44.0 20.0 2.0 mill 3.0 min 0.01 milx 1.0 UiJlnax
Nickel Base 'ron-Chromium·Molybdenum Alloys
CHLORIM£T" 3
ILLIUM' alloy to
I
60.0
56.0
2.0
6.5
18.0
22.5
JUt
U
-$.5 0.01ma1l
0.20
1.0
0.65
1.0
1.25
-
-
Nickel Base Molybdenum Alloy .'
cHt.o,nMII!T· 2
Nic,kel Base Sitleon Alloy
63.0 3.0ma. - 32.0 - 0.15 IIIa~ 1.0 1. 0 -
"AS.TEL~OY· alloy D 82.0 2.0lllllx 1.0 rna. - 3.0 O.l?max 90 0.5·1.25 Co 1.5 max
Nickel Alloyed Cast Irons
NI·Res)st Type 1
HI·Ru;st Type 2
15.5
20.0
69.0
70.0
2.2
2.2 -- 6.5
05ma.
2.8
3.0 max
2.0
1.9
1.2
1.2
_.-
--
---
HI-Resist Type 3 30.0 62.0 3.0 O.Sma. 2.6ma. 1.5 0.6
Ni·Resist Type 4 30.5 55.0 5.0 0.5 rna. 2.6 mal 5.5 06 -
--
Ni·Resist Type D2 20.0 72.0 2.1 3.0 max 2 ..f 0.9 --
HI·Resist Type D3 30.0 61.0 3.0 - 2.6 max 2.2 O.Sma. -
(1) An improved version of this alloy. CARPENTER'" stainless',No. 20Cb·3. has replaced CARPENJ£R'" ~ta'nie~s No. 20
(2) An improved version of this alloy. HASTEllOY· alloy C·276. has replaced ..ASTUt:OY· alloy C.
(3) Cast Alloy 20 alloys such as DUR,MUO alloy 20. ALOYCO" alloy 20. etc•
• See ins;de back cover for registered trademarks.

2
 Corrosion Resistance of Nickel and Nickel-Containing
Alloys in Caustic Soda and Other Alkalies
PART I. INTRODUCTION
Caustic soda (sodium hydroxide) is the most
widely used and avaBablealkaline material. In the
United States almost all of the caustic soda is pro-
duced as a co-product in the production of chlorine
by the electrolysis of sodium chloride. The elec-
trolytic cells used can be divided into two general
types: mercury cells and diapllragm cells. With
mercury cells,high purity SOt;(. caustic is pro-
duced directly, whereas with diaphragm cells. the
caustic concentration produced is within the
range of 9 to 15 per cent, and has to be further
purified and concentrated before sale. A small
amount of caustic soda is produced by the lime-
soda proce$S which WaS formerly the prime source
for this chemical.
Caustic soda is generally marketed in concen-
trations of 50 percent, 73 per cent or anhydrous.
The chemical industry is the largest consumer of
caustie soda, followed by the rayon and film in-
dustries. the pulp and paper industry and the
aluminum industry.
A large number of alloys can be used for han-
dling caustic soda, and selection is based upon
such factors as concentration. temperature, im-
3
purities in the caustic, the necessity for product
purity. corrosion rate, susceptibility to stress-
corrosion cracking (caustic embrittlement) and
economics. Caustic soda can be handled in cast
iron or steel equipment at low· temperatures. if
iron contamination is not detrimental to end use.
At elevated temperatures, however, iron and steel
are subject to caustic embrittlement and high cor-
rosionrates. Plant and laboratory tests and oper-
ating experience over many years have demon-
strated that nickel and nickel alloys are the
preferred materials for handling caustic solu-
tions in many applications. Nickel can be used for
practically an concentrations and temperatures.
In addition to caustic soda. several other im-
portant alkalies are discussed in this bulletin. but
no attempt has been made to be all-inclusive.
Nominal compositions of alloys referred to in
the text are shown in Table L Materials other
than nickel-eontaining alloys included in a num-
ber of tests are reported for reference purposes.
An corrosion rates are reported as mils pene-
=
tration per year (mpy). (1 mil 0.001 inch.)
Fig. 1 - These caustic soda evaporator units are a
combination of both solid Nickel 200 and steel clad
with Nickel 200. Diaphragm cell liquor feeds into the
double-effect evaporator: overflow from a settler tank
feeds the single'effect evaporator for conc.entration to
50% caustic soda. The system produces 700 tons of
salt and delivers 434 tons of NaOH (100%1 per day.
Ph%qraDh by courtesy ot
the Swenson Division Of Whiting Corporation.
 PART II. CORROSION BY CAUSTIC SODA

A. Nickel
1. Effect of Concentration, Temperature
and Carbon Content
Corrosion test results for nickel in commercial
caustic soda solutions were obtained by a number
of investigators at different times and locations.
Typical test data are shown in Table II and these
have been incorporated in the isocorrosion chart,
Figure 2. Only at high caustic concentration near
the boiling point does the corrosion rate exceed
one mil per year. This isocorrosion chart is in-
tended only as a guide; there are specific condi-
tions under which higher or possibly lower cor-
rosion rates can prevaiL These conditions are
discussed later.
700 r - - - . . , . - - - - - r - - - r - - - - . . , . - - - " r " > 371

600 316
Fig. 3 - View of caustic transfer piping from marine storage
tank area to terminal where rayon grade 50% caustic soeta
is loaded into a barge. Several hundred feet of lightweight.
welded Nickel 200 piping in 8-inch and 12-inch sizes are
500 ]60
used.

..:;
u... 4 oo In caustic concentrations above 75 per cent and
including molten caustic soda. nickel is second
"0
Q;
Q only to silver in resistance to corrosion. When
~ 100
f- nickel is to be used at temperatures above 316 C
(600 F). a low-carbon grade, Nickel 201 (0.02% C
max). should be employed to preclude the possi-
200 '13
bility of graphite precipitation in the grain boun-
<OJ mpy
"- 0.1 mpy daries and a resultant loss in ductility. Nickel 201
100 38
is often used for the construction of tubular evap-
orators for continuous vacuum concentration of
caustic soda from 50 and 73 per cent to anhy-
o '--_ _....l.-_.L---l._ _- - ' ' - -_ _...L-_ _ ~ •. 17.8
drous at temperatures up to 404 C (760 F). with
o 20 40 60 80 100
nickel pickup in the finished caustic of only one
to two ppm. 3
Fig. 2 -Isocorrosion chart for Nickel 200 and Nickel 201 Molten caustic soda has been considered as a
in sodium hy~roxide.l
heat transfer medium for nuclear energy appli-
Some tests which have been carried out at cation. In static tests at Harwell in England,
elevated temperature and pressure in autoclaves Gregory. et aL.~ concluded that Nickel 201 was a
indicate satisfactory performance for nickel in satisfactory container material for molten caus-
caustic soda solutions even above the atmospheric tic soda at temperatures up to 580 C (l076 F)_
boiling point, as shown in Table IIU Some of their data are shown in Table IV.

4
 Table II

Typical Corrosion Test Data for Nickel and High Nickel Alloys in Caustic Soda Solutions

Corrosion Rate, mils per year

Nickel- Nickel-
Copper Chromium
HaOH Alloy Alloy
;oncen- Temperature Test (MONEL ltNCONEl
tration, Period, Hicke! alloy alloy
% C F A.e1ation Agitation days Comments 200 40ll) 6nO\
D-1 3{l 86 Nooe Hone 27 Test coupons removed,
cleaned and dried each day
fOf lOdays 0.01 0.01 nW
4 30 86 Hone None 1&2 Average of tests run at
8 separate laboratories 0.05 0.16 -
4 3{l 86 Air agitated Air agitated 1&2 Average of tests run at
8 separate laboratories 0.05 0.21 -
5-10 21-32 70-90 Extensive due to 124 Storage lank 0.15 O.ll 0.05
filling tank
14 88 190 None None 90 First effect of multiple-
effect evaporator 0_02 0.05 0.03
22 50-60 12{)-140 None due to 133 Storage tank coupons
filling tank immersed 95% of time nil 0_01 0_01
34 65 150 Extensive Mild 37 Storage tank in which air was
bubbled through from bottom 0.03 - 0.03
30"50 81 178 None None 16 Single-effect evaporator_
Rates are average of 3 tests 0.09 0.19 -
49-51 55-75 131-167 None due to 30 Storage tank coupons
31165 av 149 lining tank fully immersed 0.02 0.03 0.02
50 55-61 131-142 None due to 135 Storage tank 0.02 0.02
31158 a1l 136 0.02
filling tank
50 60-70 14~158 Moderate by lOOgpm 393 Transler piping. at pump
av65 al/ 149 flow from discharge 0.07 0.10 0.03
pump
50 150 302 None None 14 laboratory test on tubing;
average of 4 coupons - - 0.25
72-73 116 273 None due to 183 Storage tank 0.3 0.7 0.4
filling tank
72 121 282 Moderate due to 119 Storage tank OJ 0.3 0_1
filling tank
73 95-100 203-212 None by rocking 111 rest tank_ simulating action
of tank of tank car 0.13 0.16 0.14
73 100-120 212-248 None due to 52 Storage tank coupons
avll0 a1l230 filling tank immersed 95% of time 0.05 0.04 0.06
13 104-116 244-251 None due to 126 Storage tank coupons
av 110 av248 filling tank lully immersed 0.02 0.10 0.0\
14 130 266 Not specified by movement II trips Coupons in railroad
of tank car of 7-9 tank car 0.3 0.4 -
days
15 135 271 Not specified due 10 35 Storage tank between
filling tank evaporator and finishing pots.
Ammonia Soda Process 1.6 1.7 1.3
60 to 15~260 302-500 None None 2 Concentration in caustic
nearly evaporator 3.9
anbydrnus 13.4 -

• Less than 0.005 mils per year.

5
 Table llt
laboratory Corrosion Tests in Caustic Solutions at Elevated Temperatures

NaOH Corrosion Rate, mils per year

Concen- Temperature Test MONEL WORTHITE sIs Hi-
tration, Period, Nickel alloy (solution Resist Cast ACI
% C F hr 206 400 quenched) Type 2 CN·7M
20 110 262 15 nil
40 110 262 15 nil
60 llO 262 15 nil
80 110 262 15 nil
20 115 272 19 nil
40 115 272 19 nil
60 ll5 272 19 nil
80 US 272 19 nil
20 162 355 19 nil
40 162 355 19 nil
60 162 355 19 nil
80 162 355 19 nil
20 149 332 19 nil
40 149 332 19 3
60 149 332 19 1
20 132 270 ]9 4
40 132 270 19 9
GO 132 270 19 1
80 132 270 19 nil
20 111 340 19(2 tests} 25,69
40 111 340 19 (2 tests) 36.28
60 l7l 340 1912 testsl 2,38
80 17l 340 19 (2 tests) nil. nil
20 156 345 20 14
40 156 345 20 17
GO 15G 345 20 33
86 156 345 20 1
20 127 293 15 94
40 127 293 15 6
GO 127 293 15 17
80 127 293 IS 28
20 150 334 18 10
46 150 334 18 1
GO 152 336 19 12
20 183 394 15 nil
GO 183 394 15 151
80 183 394 15 2

2. Effect of Velocity 3. Effect of Aeration

Velocity has little effect on the corrosion rate of
nickel in caustic at temperatures below 500 C
(932 F) but at 540 C (1004 F) and above, increas-
ing velocity may cause a several-fold increase in
the rate of attack. Figure 4 shows the results of
two-week laboratory experiments by Gregory,
et al., in high temperature molten caustic soda
under dynamic conditions.
Aeration has not been observed to accelerate
corrosion in lower concentration caustic soda
solutions. However, at high concentrations and
temperatures, such as occur when concentrating
to anhydrous, precautions should be taken to
minimize aeration.

6
 taining atmosphere in the vicinity where corro-
M"lten Coust;c Sodo 720 C (1328 Fl sion is occurring. Forestieri and Lad found that,
480 as a result of the presence of chromite ion
(CrO:I- 1 ) , mass transfer and cOITosion were
400 essentially eliminated for 50 hours by one per
>-
~ 680 C (1256 Fl cent addition of 325-mesh chromium powder in

.----------
E 320
a test loop operating at a fluid velocity of 15 fps
~
0
oc and 816 C (i500 F) with a temperature difference
c 240
_Q of either 11 C (20 F) or 22 C (40 F) .>1.9 However,
E
(; 635 C P 175 Fl a small mass transfer deposit was obtained after
u •
• 250 hours, indicating that a single chromium ad-
600 C {I I 12 Fl 400 C ( 752 FI dition would not protect a nickel system in-
580 C {1076 Fl 500 C I 952 F)
540 C (l004 F) definitely.

100 200 300 400 500 600 5. Effect of Impurities

Rotot;on $peed_ rpm
Chlorates in caustic can increase corrosion rates
Fig. 4 - Corrosion rate of nickel as a function of rotational
speed.'
as indicated in the later section on caustic soda
manufacture (page 27). Small amounts of so-
Table IV dium chlorate are produced in electrolytic dia-
Static Corrosion Rates of Nickel and Nickel Alloys phragm cells. The effect of the chlorate on corro-
in Molten Caustic Soda sion rate is not critical unless the chlorate is de-
composed. and thermal decomposition does not
Corrosion Rate, mils per year occur below a temperature of 260 to 290 C (500 to
Temperature 554 F). If it is intended to operate nickel equip-
460e 500e 58fl e 680e ment at or above this temperature range. four
Alloy (750 f) (932 f) (1076 f) (1256 f)
alternatives are available:
Hickel20t 0.9 1.3 2.5 37.8
a!toy e
a. Use "rayon grade" caustic which has a speci-
HASTELLOY 100.5
HASTELt.OY aUoy D 0.7 2.2 9.9 fication of 5 ppm maximum chlorate content.
MONEl. alloy 400 1.8 5.1 17.6 b. Use caustic produced by electrolytic mercury
INCONEL aUoy 600 U 2.4 5.1 66.4
OURANICKEI. alloy 30t 1.7 3.2 10.4 40.7
cells or by the lime-soda process, or,
NIMONIC all01 75 1.1 14.3 20.8 47.6 c. Use anhydrous caustic; there are no chlorates
(pitted)
in the anhydrous grade.
• Gained weight. Swollen outside surface largely oxide-heavily cor·
roded. d. Add reducing agents as discussed in the sec-
tion on caustic soda manufacture (page 27) .
4. Effect of System Thermal Gradients The presence of oxidizable sulfur compounds
In molten caustic soda at temperatures above in caustic soda tends to increase the corrosion
about 550 C (1022 F), nickel is subject to thermal rate of nickel at elevated temperatures. This is
gradient mass transfer.:;· 4;. 7 In this type of at- noted particularly with hydrogen sulfide, mer-
tack, nickel is dissolved in caustic at a high tem- captans, or sodium sulfide, and to a much lesser
perature surface and is precipitated at a low extent with partially oxidized compounds such as
temperature surface in a circulating system. thiosulfates and sulfites.
Gregory, et at, concluded that the corrosion rate The effect of the addition of oxidizable sulfur
of nickel in molten caustic soda could be ten times compounds to caustic soda on the corrosion rate
as great under dynamic conditions as it was of nickel has been studied in the laboratory with
under static conditions because of the solubility- the results shown in Table V. Test 1 was made
temperature relationship.:; during the evaporation of a commercial caustic
The mass transfer effect can be inhibited but soda solution under 28 inches of vacuum. Sulfur
not prevented by maintaining a hydrogen-con- content of the original caustic. calculated as per

7
 Table V (Nickel 201) will circumvent this problem.
Applied or residual stresses apparently do not
Effect of Oxidizable Sulfur Compounds on Corrosion
of Nickel 200 in Caustic Soda significantly affect the genera! corrosion rate of
nickeL 11
Temperature: 130 C c::: 5 C (266 F c::: 9 Fl.

Corrosion 7. Effect of Dissimilar Metal Contact

Test
No. Corrosive
Commercial Sodium Hydroxide being concentrated
from 50 to 75% NaOH (Sulfur content at start.
calculated as H,S. 0.009%}
2 75% C.P.· Sodium Hydroxide
3 75% C.P. Sodium Hydroxide plus 0.75% Sodium
Sulfide
4 75% C.P. Sodium Hydroxide plus 0.75% Sodium
Th~wlf~e
5 75% C.P. Sodium Hydroxide plus 0.75% Sodium
Sulfite
6 75% C.P. Sodium Hydroxide plus 0.75% Sodium
Su!!ate
Rate,
mils per year Galvanic corrosion can occur in caustic soda solu-
tions if different materials of construction are
electrically connected. Whether this effect is aca-
1.7
demic or critical depends upon the specific condi-
0.6
tions that exist in a partiCUlar installation. For
22.8 instance, the data in Table VII illustrate that gray
cast iron corrodes from about one and one-half
~9
Table VI
5.2 laboratory Tests in fused Caustic Soda with and
without Addition of 5% Sodium Peroxide
0.6

• Chemically pure. Temperature Metal Pickup. grams

COHosive C f Nickel Imn Copper
cent H;!S in dry caustic, was 0.009 per cent. Test 2
was made in chemically pure caustic soda. Tests 3 Caustic Soda 350 662 .4
360 680 .01·.02
through 6 were made in chemically pure caustic
400 752 Irace·.02 .426
to which the various sulfur compounds had been 450 842 .01·.02 .2·.3
added. 500 932 .005·.015 .2·.3
550 1022 .4·.43
It has been found that the detrimental effect
600 1112 .i3·.3
of oxidizable sulfur compounds in caustic can be
Caustic Soda 350 662 .0024 .024 trace
counteracted by the addition of sufficient sodium
with 5% Sodium 400 752 .0135 .025 .013
peroxide to form sulfates. An excess of peroxide Peroxide 450 842 .OBI .Il .03
does not seem to be detrimental. as shown in
• SI rangly attacked
Table VI which compares the resistance of nickel,
Table VII
iron, and copper to fused caustic soda with and
without an addition of 5c;. sodium peroxide. lo Galvanic Corrosion of Gray Cast Iron
In each test, 5 grams of the substance were fused Conditions: Corrodent: 5% sodium hydroxide.
for four hours in a laboratory crucible of the Temperature: 43 C (ll 0 F).
given metal and analyzed for metal pickup. Flow: 16 feet per minute.
Aeration: Saturated WIth air.
Cathode to anode area ratio 2: 1.
6. Effect of Stress
Experience has indicated that Nickel 200 is not Corrosion Rate of Corros ion Rate of
subject to stress-corrosion cracking in pure Gray Cast Iron. Cathodic Material,
mils per year mils per year
caustic solutions. However, it is subject to In In
stress-corrosion cracking by mercury, and there Cathodic Galvanic Galvanic
Material Insulated Couple Insulated Couple
have been a few cases of cracking of nickel when
"upsets" occur in producing plants that utilize Nickel 200 l.l 1.5
Nickel 200 0.6 ]6 0 <0.1
mercury cells.
MONEL alloy 400 0) 2.1 <01 <0.1
In addition, cracking along precipitated grain MONEL alloy 400 0.6 17 0 0
boundary jTraphite in Nickel 200 has occurred 0.75 1.72
after caustic soda exposure above 316 C (600 F). Average Average
As indicated previously. a low-carbon grade • Slight welgh1 gain

8
to three times its normal rate when connected to 8. Cathodic Protection
Nickel 200 or MONEL alloy 400, under the given In the continuous production of anhydrous caus-
set of conditions. However, the normal rate for tic, experience has shown that cathodic protection
cast it-on in 5~-;' caustic is so low that these higher can be applied successfully to nickel evaporating
corrosion rates are usually tolerable. equipment. In one such case, a cathode current
At higher caustic concentrations, tempera- density of about 1 ampere per square foot of ex-
tures, and with large cathode to anode r;:ttios. posed nickel surface provided satisfactory pro-
galvanic corrosion becomes more pronounced. tection. In other less corrosive applications, as in
The galvanic current curves shown in Figure 5 storage of 75~(· caustic, current densities as low
are from tests made above and close to the upper as 0.01 ampere per square foot have been reported
tube sheets of operating caustic evaporators. The effective. Nickel 200 anodes are used in these ap-
general conclusions to be drawn from these tests plications_ Laboratory tests in 75% caustic soda
are that in concentrated caustic soda solutions. at 120 C (250 F) and also in fused anhydrous
significant galvanic corrosion may occur on cast caustic soda at 480 C (900 F) have shown that
iron or steel when in contact with nickel or cop- \",ith equal areas of nickel for anode and c.athode,
per. In the construction of caustic evaporators. and with an applied anode current density of
it is desirable, if not actuaHy necessary, to use 10 amps per square foot, the corrosion rate of
nickel or nickel-clad steel tube sheets in conjunc- the nickel anode does not exceed that of uncoupled·
tion with nickel tubes. nickel. A pure technical grade of sodium hydrox-
70r---~----'----r----.----r----'----r---. ide was u~ed in these tests, which contained less
u.
q
GoJvonrc Current Flow Between
than 0.04 per cent of heavy metal impurities. The
~ b.O C05-t 1£on end Copper result.c; are shown in Table VIn.
~ 5.0 A"'?oe: c.,;~ !"on Ar~" . C 3QS -;:: ;:.
C,~d~ode: Ccpoe r A~e'1 0.*9"4 ;-:: =.
t Table Viti
Si 4.0
c
~
laboratory Tests of Nickel 200 Anodes and Cathodes
{; 3.0
o" in 75 Per Cent and Fused Caustic Soda
Temperature: 120C (250F) for 75% caustic.
480 C (900 F) for fused caustic.
" 1.0
~
Duration of Tests: 18·21 hr.
.(
Volume of Solution Used: 1 liter.
JS Anode Current Density: 10 amp per sq ft.
Area of Specimens: 0.066-0.087 sq ft.
7.0,-----,..-----,----,..-----.--__-,-____,--__-,-__--,

Average Corrosion Rate.

Golvonic Cv ...enf flow Between mils lIer year
Cad Iron ond Niclel
75% Caustic fused Caustic
A"\Cd:~: C~S~ h,)~ Af"-e:2 =-.C c.J~a ~ J c.
C,+ode: N;d:e~ Are~ ...:. il.24; 5.;)::.
Nickel 200 Anode 0.8 11.3
Nickel 200 Cathode 0.2 0.9
NickeI200-Uncollpletl 1.0 11.2
~

.~ 3.0
0

?" 2.0
Note that the cathodic nickel surface benefited
U
"
"D 1.0 from cathodic protection, while the corrosion rate
.(" of the nickel anode was not increased.
0
Q S

Fig. 5 -- Current measurements between cast <ron, copper

and nickel specimens set up above and near the upper tube
sheet of an evaporator concentrating caustic soda from 47
to 60 per cent. NaOH under 26 in. vacuum using steam at
a pressure of 75 Ib per sq in.
B. Nickel-Chromium Alloys
Nickel-chromium alloys, such as INCONEL alloy
600, are approximately equi\'alent to nickel in

9
corrosion resistance in caustic soda, as shown in
Tables II, IV and XL.
Alloy 600 is commonly used in equipment for
the production of anhydrous caustic when sulfur-
bearing fuels are used for heating because it is
more resistant to sulfidation than nickel.
There have been a few instances of stress-
corrosion cracking of Alloy 600 in some strongly
alkaline environments. A review of these serviee
failures has indicated that they usually occurred
in concentrated caustic solutions at high tempera-
tures, 190 to 450 C (374 to 842 F). In seven-day
laboratory tests, caustic concentration, tempera-
ture, and the presence of air were shown to be
important variables, as shown in Tables IX and
XIV. No stress-corrosion cracki ng occurred if the
Fig. 6 - This barge has eight tanks with a capacity of
Alloy 600 U-bend specimens were stress-relieved 34,000 barrels.. The tan~s are used to carry fuel oil or as·
at 900 C (1650 F) for one hour or 769 C (1400 F) ph~lt. and a specli;ll 54.00·barret tank fabricated of INCONEl
alloy 600-clad steel is used to carry 73 010 caustic soda, am·
for four hours after bending. monia·basefertilizers, or jet fuels.

higher than nickel at temperatures above the

Table IX atmospheric boiling point, as shown in Table III.
Stress·Corrosion Cracking of INCONEl Alloy 600 However, it should be noted that even in those
U-Bend Specimens in Caustic Solutions- cases where AHoy 400 is inferior to nickel, the
Seven-Day Tests corrosion rates are still quite low.
There have been a few reports of stress-corro-
Temperature Over- Caustic CORcentratiolt, weight % sion cracking of cold-worked and stressed Alloy
pressure.
C f 150 psi Caustic 10 50 90 400 in caustic soda. However, the eXact conditions
200 390 Air NaOH OK OK
under which most of these failures occurred are
250 480 Air NaOH stress-cracked not known. It is known that some of the reported
300 570 Air NaO" OK stress·cracked stress·cracked failures associated with mercury cell caustic were
200 390 Argon NaO" OK OK caused by intergranular attaek by mercury and
250 480 Argon NaOH OK
subsequent loss of ductility.
300 570 Argon NaOH OK OK OK
Laboratory tests have shown that Alloys 400
200 390 Air KOH OK slight inter·
granular and K-500 can be susceptible to stress-corrosion
penetration cracking unde.r extreme exposure conditions. that
250 480 Air KOH stress·cracked
300 570 Air KOH OK OK stress-cracked is, high stresses in combination with high tem-
peratures and concentrated caustic soda can cause
Note: Testing performed in autoclaves under static conditions without
replenishment of air or argon. cracking. Table X shows the results observed
with tensile loaded specimens tested at 300 C
(570 F) in condensing steam after being coated
with either potassium or sodium hydroxide.
C. Nickel-Copper Alloys Under these exposure conditions, Alloy 400,
Nickel-copper anoys, such as MONEL alloy 400, which had been cold-worked or cold-worked and
are practically as resistant to caustic soda as stress-relieved prior to testing, was susceptible
nickel, as shown in Table II. to stress-corrosion cracking~ cold-worked mate-
The corrosion rate of Alloy 400 is higher than rial that had been annealed at 850 C (1560 F) or
nickel at caustic soda concentrations above 75 per 950 C (1740 F) prior to testing was resistant. As
cent when concentrating to anhydrous. It is also with Alloy 400. Alloy K-500 cracked when cold-

10
 Table X
Stress-Corrosion Tests on MONEL Alloy 400 and MONEl Alloy K-500

Type and Degree of

Yield Applie II Cracking
Strength, Stress,
Alloy Heat Treatment ton/ S1l in. tonI sq in. NaO\( KO\(

MONEL alloy 4(1(1 None-as cold-drawn 43.8 33.1 IIG 41'11

850 C (1562 fltIti hr/W.O. 12.8 16.3 5 5
MONEL alloy 40(1 Stress relieved
540 C 11004 fl/ ¥z hr 24.0 20.1 OIG OIG
MONEL alloy 40(1 Works anneal·
950 C U742 fll Y2 hr 11.4 8.3 5 5
MONEL alloy K·S(I(I None-as COld-drawn 52.5 33.1 3IG+TG 5
870 C U598 f)f5 min/W.O. 21.2 10.3 5 5
580 C(1076 fl/S hf/fC· 65.5 37.2 4TG 5
810 C US98 A/S min/W.O.
+ 580 C{1016 fl/16 hr/FC· 44.9 37.2 OrG OIG
MONEL alloy K·500 None-as cold·drawn 53.2 33.1 4NI
870 C(1598 fl/5 min/W.O. NO 10.3 5
580 C n076 AIS hrl FC· NO 37.2 OIG
870 C (1598 fl/5 min/W.Q.
+ saocno76 flfl6 hr/fe· NO 37.2 DIG
• Fumace-coaled at about 10 C (18 Fl/nr to 480 C 4 = Shallow cracks visible under microscope
(896 Fl then "if.-coa!ed to room lef'lperature. 5 = No cracks
NO = Not Determined TG = Transgranular cracks
o == Specimen fractured IG == Intergranula. cracks
1 == Coarse 'cracks visible to naked eye I'll = Type of cracking nQt jdentified-cracks very
2 == Fine cracks visible to naked eye short.
3 == Deep cracks visible under microscope

worked and was resistant in the annealed condi-

tion. However. the thermal-hardening treatment >-
0-
at 580 C (1076 F) rendered the alloy very suscep- E
tible to cracking. o'" 12
a::
The practical interpretation of these data is 5 8
.;;;
difficult because threshold values of stress, caustic l?
soda concentration, and temperature at which ~ 4

stress-corrosion cracking will occur have not been

established. With these limitations in mind, it 20 40 60 100

would appear prudent to stress-relieve AHoy 400 Per Cent Nidel in Copper.Nickel Alloys

in the range of 538 to 566 C (1000 to 1050 F) or
anneal it ill the range of 760 to 816 C (1400 to
1500 F) for one to three hours when it is to be
used in higher strength caustic at elevated tem-
peratures.
D. Copper-Nickel Alloys
The corrosion resistance of copper-nickel alloys
in can.stic soda solutions is dependent upon the
nickel content of the alloy, as illustrated in Fig-
ure 7. There are a limited amount of additional
data which are shown in Table XI.
Fig. 7 - Results of corrosion tests of copper-nickel alloys
in 50% caustic soda evaporator.
Copper-nickel alloy CA 715 (70% Cu-30% Ni)
possesses excellent resistance to dilute concen-
trations of caustic soda at low temperatures and
appears to have useful resistance to caustic soda
solutions of up to 73 per cent at the boiling point.
However, this resistance does not extend to fused
caustic. Alloy CA 715 has been used successfully
as evaporator tubes for concentrating to 50 per
cent where copper pickup by the caustic could be
tolerated.
Copper-nickel alloys CA 706 (90(~ Cu-lO('~ Ni)

11
 Table XI
Corrosion of Copper-Nickel Alloys by Caustic Soda Solutions

Nominal
Alloy
HaOM Composition Test Corrosion
Concen- Copper- Temperature Dura- Rate,
tration, Hickel Wt% Wt% tion, mils per
% Alloy Cu Hi C F days year Comments

5 - 60 40 15-20 I 59-68 21
25
Nil·
0.5
laboratory test in glass bottle.
Diaphragm cell liquor·
11 60 40 Hot-Exact temperature
unknown coupons in distributor box to settlers.

5 70 30 15·20 .1. 59-68 21 Nil laboratory test in glass bottle.

11 70 30 Hot-Exact temperature 25 4.3 Diaphragm cell liquor·
unknown coupons in distributor box to settlers.
50 70 30 95 203 67 0.8 Velocity 1.8 ftl sec. Salt saturated.
50 CA 715 70 30 65 149 30 Nil In storage tank.
73 70 30 105 221 118 1.2
60-75 70 30 150-175 302·347 l/Z 4.4 In evaporator concentrating from 60-75%.
60-1Im 70 30 150·260 302·500 2 21 In evaporator concentrating
from 60% to anhydrous.
100 70 30 400·410 752·770 1 70 In anhydrous melt.

5 80 20 15·20 59·68 21 Nil laboratory test in glass bottle.

60·75 80 20 150-175 302·347 liz 8.1 In evaporator concentrating
CA 710 from 60·75%.
60·100 80 20 150·260 302·500 2 28 In evaporator concentrating
from 60% to anhydrous.
100 80 20 400·410 752·770 1 90 In anhydrous melt.

50 90 10 95 203 67 1.8 Velocity 1.8 ft/sec. Salt

CA 706 saturated.
73 90 10 105 221 118 2.0
,. Less than 0.1 mit per year.

and CA 710 (80% Cu-20% Ni) have useful resist- Table XII
ance to caustic soda solutions but their applica- Corrosion Rate of Copper-Nickel Alloy CA 715
tion is limited to lower concentrations and tem- in Alkaline Solutions Containing Sulfur Compounds
peratures than AHoy CA 715. Because of the
Corrosion
limited data available it is difficult to define limits Duration, Rate,
for these two alloys. Conditions of Exposure days mils per year
While corrosion of the copper-nickel alloys by 1. In open tank used to boil 18·22 per cent
caustic solutions may be aggravated by the pres- NaGH to release mercaptans at 80 C (175 fl 30
ence of sulfur compounds, Alloy CA 715 is able 2. In reboiler of caustic stripper, 1·2 per cent
NaDH.3 per cent Na,S. 10 per cent sodium
to resist attack under some conditions, as shown phenolate + 0.7 mg per liter as sodium
mercaptides at 124 C (255 Fl 131 25·
in Table XII. No data appear to be available on
3. In 10 per cent sodium sulfide in storage
the susceptibility of these alloys to stress-corro- tank at atmospheric temperature 81
sion cracking in caustic soda solutions. 4. In 60 per cent sodium sulfide in flaker
feed tank at 171 C (340 f) 28 14
5. In regenerator reboiler for steam stripping
of mercaptans from solutizer solution
25.2 per cent potassium hydroxide
37.8 per cent potassium isobutyrate
5.5 per cent potassium sulfide
1.9 per cent potassium mercaptides
2.1 per cent potassium carbonate
at 141 C (286 f) 140 15
6. In vapors from solution in item 5 140 12
~ Pitting up to 3 mils depth.

12
 E. Iron·Nickel·Chromium Alloys Table XIV
Based upon data obtained in several test expo- Laboratory Tests-Results of U-Bend
sures and shown in Tables Xln and XL, it appears Specimens in 90% Caustic Soda at 300 C (572 F)
that INCOLOY alloy 800 approaches INCONEL alloy Maximum Depth of Cracks, mils
600 in resistance to caustic soda. However, Alloy Argon 15 psig 50 psig 150 psig
800 is more susceptible to stress-corrosion crack- atm. air air air
Material 1 week 1 week 8 weeks 1 week
ing than Alloy 600, as shown in Table XIV.
There has not been sufficient experimental INeOLOY alloy 800 10 7 120lal 1151bl
work on the stre.ss-corrosion cracking of Alloy INCONEL alloy 600 0 0 75 115
Type 304
800 to determine if stress-relieving in a tempera- Stainless Steel 100 110 11 10
ture range which will cause sensitization (pre- (a) Removed at four weeks.
cipitation of chromium carbides in a continuous (b) Two·week test.
Note: Testing performed in autoclaves under static conditions without
network) renders the alloy more susceptible to replenishment of air or argon.
this form of attack. Therefore, it would appear
prudent to anneal the alloy in the range of 1120 to
1150 C (2050 to 2100 F) or stress-relieve and sta-
bilize at 870 C (1600 F) for one to two hours when
it is to be used in higher strength caustic soda
at elevated temperatures.

Table XIII
Plant Tests-Corrosion Rates in Caustic Production Equipment Using Electrolytic Diaphragm Cell Caustic

(. Exposure times vary from 24 to 29 days

Conditions Corrosion Rate, mils per year

'"
'"
= '"
'"
= ~
~
~
~
~

~
.,.'"'" ~
:s~
~

:'§a;
~

:Sa:;
M
~

"'",. ~

" !9~ ~~ .e.e

.,. ~
~

'""z '"
NaOH NaGI
Temperature '"
'"
N
~ .,.
<n<n
.,.
<n<n <n<n
~
] c
0 W .;;; 1':
Concen- Concen· Av Max Min ~
0
0;
~
w Z
0
'"
M '"
M '"
M
~
t;
tration, tration, ~ ~ ~ ~ ~

G F G F C F "~ ~

Z
0
"~ ~
~ ~
~
~
~ '"
.~
z " ~
~
% %
"'
~ ~ ~ ~

10 12 88 190 91 195 82 180 <0.1 <0.1 <0.1 <0.1 0.2 <0.1 0.2 0.2 5 4
23 J.8 93 200 104 220 82 180 0.2 0.1 0.3 0.1 0.4 2 0.4 1 9 2
35-40 6·7 116 240 127 2~0 102 215 0.6 0.4 1 0.5 1 2 0.9 3 46 49
50 10·15 93 200 104 220 71 160 <0.1 <0.1 0.2 <0.1 0.2 0.2 0.4 0.4 5 6
72 ? 121 250 124 255 119 245 0.1 <0.1 OJ <0.1 4 3 0.3 5 4 16

concentrated solutions and at higher tempera-

F. Austenitic Chromium-Nickel
Stainless Steels
Austenitic chromium-nickel stainless steels offer
good corrosion resistance to boiling caustic soda
solutions up to about 10 per cent concentration,
but from 10 to 50 per cent, the temperature for
satisfactory service probably would not exceed
93 to 100 C (200 to 212 F). Generally more severe
but inconsistent corrosion rates occur in more
tures. An isocorrosion chart (Figure 8) sum-
marizes the corrosion behavior of austenitic
stainless steels in caustic soda.
Typical corrosion rates for several stainless
steels are shown in Tables XV and XL. Type 316
stainless steel does not appear to offer any ap-
preciable improvement in corrosion resistance
over Type 304 stainless steel in caustic soda solu-
tions.

13
 700 .-----r-------,-----r----r------.-. 3 It Therefore. post-weld heat treatment of regular
(0.08 max) carbon grades or the selection of a
low-carbon or stabilized grade of stainless steel
600 lib
does not appeal' to be required for these exposure
conditions. However, intergranular corrosion of
sensitized Type 304 stainless steel was observed
500 2&0
by Agrawal and Staehle in boiling solutions of

'-'-. 400
~
~
"
Q.
E
~lOO
\
\
\
I
\.
,
..o..pF=".Jre~·

.1\
Bo;';n9
0'
5tre~~\·CO(f·Os~O':"I
C'OC';"1 Bou"cio,y

·:""";)-~oher;.:
P;i", C~rve
30moy
20 to 80('; NaOH.I:t
Chromium-nickel stainless steels are subject
to stress-corrosion cracking in caustic soda solu-
tions at elevated temperatures. Nathorst H re-
ported several cases of stress-corrosion cracking
of austenitic stainless i3teels caused by alkalies.
to ' .......
f
50 m py A comparison of the cracking behavior of Type
200 Q) 304 and Alloys 600 and 800 is given in Table XIV.
A stress-corrosion cracking zone based upon these
.-: 1 ::npv
AU Grades
and other known failures reported in the litera-
100 19 ture is shown in Figure 8. A dashed line was used
to indicate the temperature-concentration bound-
ary because this zone is probably not completely
OL-____~--L-~----~L-----~----J 17 S defined. Agrawal and Staehle have shown that
o 20 &0 ,,-' 100
sensitized Type 304 stainless steel is more prone
than annealed material to stress-corrosion crack-
fig. 8 - Isocorrosion chart for austenitic chromium· nickel
'stainless steels in sodium hydroxide, ing in boiling caustic sodaP A portion of their
data is shown in Figure 9. The cracking obtained
J. M. Stone observed that Type 304 stainless was predominantly intergranular in the sensi-
steel sensitized for one hour at 677 C (1250 F) tized material and predominantly transgranular
was not susceptible to intergranular corrosion in the annealed material.
during 40-week exposures in: 1:!0 Commercial standard grade 50r;. caustic soda
1. 10% NaOH at room temperature from diaphragm cells can have up to 11.000 ppm
2. 10% NaOH boiling at about 102 C (216 F) chlorides. and commercial 50 c ; caustic soda from
3. 50% NaOH at room temperature. and mercury cells and reagent grade anhydrous caus-
4. 50% NaOH at 60 C (140 F). tic can have up to 50 ppm chlorides. It has been

Table XV
Corrosion of Stainless Steels by Caustic Soda Solutions

HaOH
Concel!- Temperature Test Corrosion
AISI tration. Duration. Rate.
Type % C F days mils per year Comments

302 20 50·60 122·140 134 <0.1 storage tank

309 20 50-60 122·140 134 <0.1 storage tank
310 20 50-60 122·140 134 <0.1 storage tank
304 22 50..60 122·140 133 <0.1 storage tank
309 34 65 149 37 <0.1 storage tank
310 34 65 149 37 <0.1 ;Iorage tank
309 50 21 70 134 <001 storage tank
3to 50 21 70 134 <0.1 storage tank
202 50 50·65 122·149 167 0.5 storage tank
304 50 50..65 122·149 167 <01 storage tank

14
 10'
L

~
'".}
j
10

So;\;"9 So:"·<,~;
lcood JOO e "_ ~J Y e':i >'tres,"

,O','="O----::l:?O=----=li:-O--..-'=0---SOL----/,L.O---L70---180

Fig. 9 - Stress·corrosion cracking of annealed and sensi·

tized Type 304 stainless steel in caustic soda solutions. l3

suggested that unreported chloride impurities Fig. 10 - Piping and certain internal parts of these two
KAMYR ¢ digesters used in the pulp and paper industry are
are responsible for some of the stress-corrosion Type 316L stainless steel to resist caustic soda and sodium
cracking. I;; Whether the reported cracking was sulfide. Insulation sheathing is Type 304 stainless steel to
resist alkaline spills.
caused by caustic solutions or the chlorides these • See inside back cove<for registered trademarks_
solutions contain is an academic point. In any
case. consideration should be given to the tem- The authors reported that the results for ACI
perature and stress limitations of austenitic CF-8M were similar. Alloys CF-8 (cast equivalent
stainless steel in caustic soda solutions. of wrought Type 304) and CF-8M (cast equiva-
Autoclave tests have been run on some of the lent of wrought Type 316) both exhibited increas-
cast stainless steels at temperatures both above ing corrosion rates with increasing temperature.
and below the boiling point. II; Data for ACI alloy
CF-8 from these tests are shown in Table XVI.
G. Iron-Base Nickel-Chromium-
Table XVI Copper-Molybdenum Alloys
Corrosion of Cast ACI AUoy CF·8 and
in Caustic Soda at High Temperature Nickel-Base Chromium-Copper-
HaOH Temperature
Molybdenum Alloys
Concentration, Corrosion Rate Range,
% C f mils per year The limited corrosion test data for wrought alloys
such as CARPENTER 20Cb-3. INCOLOY alloy 825.
20 119 245 0·5 HASTELLOY alloy G, and cast ACI CN-7M composi-
138 280 20·50
185 365 20-50 tions in caustic soda solutions. shown in Tables
245
III, XVII and XL, indicate appreciable corrosion
40 119 0·5
138 280 20-50 resistance. These alloys fall between the austenitic
185 365 50-200 chromium-nickel stainless steels su!:h as Type 304
219 425 >200 or cast ACI CF-8 and the nickel-chromium alloys
60 119 245 5-20 such as Alloy 600 in resistance to caustic soda
138 280 50-200
185 365 50-200 solutions. They are markedly superior to Type
219 425 >200 304 stainless steel and ACf CF-8 in concentrated
80 119 245 0-5 solutions above 95 C (205 F)_
138 280 5-20 At least one plant has used WORTHITE stainless
185 365 20·50
steel pumps for handling 73('; caustic soda at

15
140 C (284 F).I' However, the same reference Table XVIII
also cites high corrosion rates for alloys of less Corrosion of HASTEllOY Alloys Band C
than 70'; nickel, which would include WORTHITE in Caustic Soda Solutions 18
stainless steel, in a storage tank handling 73'";
NaOH Temperature Corrosion Rate. mils per year
caustic soda at temperatures ranging from 120 to Concen-
tration. HASTEllOY HASTELlOY
171 C (248 to 340 F). Thus, the 140 C (284 F) ap- % C F alloy B aUoyC
plication may be at the upper limit of usefulness
for this aHoy. 5 Room Room Nil Nil
5 66 150 Nil Nil
if these alloys are to be used in conjunction 5 102 215 Nil Nil
with nickel and high nickel alloy equipment in to Room Room Nil Nil
10 103 217 <2 2·20
strong caustic soda solutions at elevated tempera-
10 121 250 2·20
tures, consideration should be given to electrical 20 107 225 <2 2·20
insulation between the dissimilar alloys so as to 25 Room Room Nil Nil
prevent harmful galvanic effects. 25 66 150 Nil Nil
30 166 240 <2 2·20
40 Room Room Nil Nil
40 128 261 <2 2-20
50 Room Room Nil Nil
50 66 150 Nil Nil
H. Nickel-Base Molybdenum or 50 144 291 <2 2·20
50 400 750 152
Molybdenum-Chromium-Iron Alloys 60 165 328 2·20 2·20
Materials such as HASTELLOY alloys Band C-276. 70 191 375 2·20 2-20
INCONEL alloy 625 and cast CHLORIMET alloys 2 Note: I) N.t means no measurable corrosion was observed in five
24·hour test periods.
and 3 have not been used to any great extent in 2) 2-20 means corrosion (ate was within this range.
caustic soda solutions. Ag a result. corrosion data
for them are rather mea~er. Tables IV and XVIII than 50 per cent C.lllnot be determined with the
show the results of some iabonltory corrOfiion exi::;ting data. HASTELLOY alloy C and INCONEL
tests. From these data. it is evident that HASTEL- alloy 625 were both found to be subject to stre::;s-
LOY alloy B can be u:~ed in concentrations up to 50 corrosion cracking in seven-day tests in aerated
per cent at the boiling point and that the tempera- 90'; NaOH at 300 C (572 F). but did not crack if
ture limit for HASTELLOY alloy C-276 would be ar~on was Sub5tituted for the air in tests at the
somewhat less than with Alloy B. Temperature Paul D. Merica Rese~lrch Laboratory of The Inter-
limitations in caustic soda concentrations ~reater national Xickel Company. Inc.

Table XVII
Iron Base Nickel-Chromium-Copper-Molybdenum Alloys
and
Nickel Base Chromium·Copper-Molybdenum Alloys
in Caustic Soda Solutions

HaOH
toncel}- Temperature Test Corrosion
tration. Period. Rate.
% C F days Comments mils per year

10 24 75 laboratory test.
INCOLOY alloy 825 <0.1
10 66 150 laboratory test.
INCOlOY alloy 825 <0.1
13 95·100 203·212 111 Test tank simulating
action of lank car.
WORTHITE stainless steet 0.2
74 130 265 II trips rest iOl tank car.
of 7·9 days CARP[NHR alloy 20 0.3·0.9

16
 I. Cast Irons and Ni-Resists
The beneficial etred of nickel additions 011 the
corro:,ioll t'esistance of cast irons in moderately
concentrated caustic alkali is shown by data in
Tables XIX, XX Hnd XX I. It is evident that nickel
contents of 20 to 30 per cent pro\'ide vet'y marked
improvement in resistance to corrosion as com-
pared 'with unalloyed cast iron. It is also apparent
that as lo'w as 3 to 5 c ; nickel may improve the
corrosion resistance of cast iron in some con-
centration ranges,

Table XIX
Effect of Nickel Additions on Corrosion Rates
of Cast Irons in 50 to 65% Caustic Soda
Temperature: Boiling under 26 in. (mercury) vacuum. Fig. 11 - Moiten sodium hydroxide at an initial tempera·
Duration: 81 days. ture of 370 C (700 F) is converted to flake caustic by this
flaker and breaker. All surfaces exposed to caustic are nickel
Corrosion Rate, except for l'li'Resist Type 3 cooling drum.
Nickel, % mils per year
Table XXI
o 73
o 91 Plant Corrosion Test in 74%
o 86 Caustic Soda in Storage Tank
3.5 47
Specimens exposed for total of 32 days (20 days in liquid
5 49 and 12 days in vapor).
15 30
Corrosion rates based on 20 days exposure to liquid.
20 3.3
20 (plus 2% Chromiuml S.O Temperature:. 125 C (260 n.
30 0.4
Corrosion Rate,
Material mils per year
In practice. the nickel cast irons most widely
MONEl. alloy 400 0.9
used with caustic solutions, where minimum con- H.i-Resist Type 3 2.5
tamination of the caustic is desired. are the Ni- Hi·Resist Ductile rron Type 02 5
Resist alloys and their spheroidHl graphite coun- Hi-Resist TYlIe 2 6
Type 304 Stainless Steel 15
terparts. the ductile Ni-Resist alloys, The corro- Mild Steel 75
sion rates of these alloys fora number of different Cast Iron 76
exposures are shown in Table XXII.
Copper-free Ni-Resist Type 2 may be used in
Table XX preference to Xi-Resist Type 1 (6.50:-; copper)
Corrosion of Nickel Cast Irons in the where it is desired to keep copper content of the
Evaporation of Caustic Soda from 37 to 50 Per Cent solution at a minimum, The 30 r ;. nickel cast iron
Average Temperature: 120 C (248 F). (Ni-Resist Type 3), in addition to having some-
Duration: 51 days. what g-rcater resistance to corrosion by hot caus-
Corrosion tic solutions than Ni-Resist TypeS 1 and 2, has a
Nickel, Chromium, Copper, Silicon. Carbon. Rate. low coefticient of expansion, an advantage for
% % % % % mils per year
expOSUI"C conditions invo!\'ing sudden changes in
28.60 1.71 1.30 2.87 17 temperature.
28.37 1.50 2.72 18
14.26 2.39 6.08 1.62 3.15 22 Of the fi\'e basic types of ~i-nesist. Type 3 ap-
19.40 1.42 3.15 24 pear:' to be the best suited to meet the require-
19.02 2.90 1.22 3.18 28 ments for caustic sen"ice. !'\i-l1e::;ist Type 3 or
20.53 1.25 2.91 31
Type D3 can be con::;idered as alternate materials

17
to nickel and the high nickel alloys for caustic
soda concentrations up to 73 per cent, but nickel
is preferred for higher concentrations.
There have been occasional stress-corrosion
cracking failures with the Ni-Resists in high-
chloride aqueous environments. Although these
environments did not include caustic soda, it
\\"ollld appear a reasonable precaution to stress-
reliew these alloys at 677 C (1250 F) for one
hour before use in hot caustic soda solutions.

Table XXII
Corrosion Rates of the Ni-Resists in Caustic Soda

Corrosion Rate. mils per year

NaOH c
Concen- Temperature Test '"
"'~
'"
";:;fN '"
'~("') '" v
"Vi ~.~~
C>

tration, Period, "'",

'70..
"'",
'70..
"'",
'70..
"'", .-
'70..
'"
~o:: ~
% C F Aeration Agitation days -x>-
>-
'"'"
. - >. . - >. . - >. =:Ii • ..!. >..
X..- 201- XI- c2O>- c..>

8.5-9 82 180 None due to 32 plus 15·15.5% 2.5 0.8 1.5 15

filling tank NaCI in storage
tank
10 88 190 Moderate due to 279 plus 12');' NaCl 0.2 4
filling tank in storage tank
I
14 88 190 None due loevap. 90 lirst eHect of ! 8
i
multiple effect !

23 93 200 Moderate Medium 48

evaporator

plus 7-8% NaCI

I 1.2 21
in salt settler
30 85 185 Moderate Moderate 82 plus heavy con- 0.8 0.4 0.1 0.5 6
centratlOn of
suspended NaG!
in sail settler
35-45 116 240 Moderate Small 24 plus 6-7% NaGI 3.3 49
in salt settler.
Intermittent ex-

49-51 55 149
posure to vapor
I
I
None due to 30 storage tank II
filling tank
50 55 131 Moderate 1.8 Ips 173 plus heavy con-
cen,ration of
0.5 0.2 I, <0.1 0.2 1.2
suspended NaC!
in transfer line
II I I
I

50 71-104 160-220 Moderate 1 Ips llS plus 10·15% NaG! OA 6

in cooling tank
50 95 203 Moderate 1.8 Ips 67 plus heavy con- 1.0 0.6 0.4 11
cent ration of
suspended NaGl
in transfer line
50 21-127 70-260 None None 10 days laboratory test 4.7 5.0
@250F
& 4 days
@70r
50-65 Boiling None due to evap. 81 30 3.3 OA 86
50-70 121 250 None due to evap. 10 in evaporator 90 290
72 121 250 Moderate very small 1]9 star age lank 4.7 15
74 127 260 Above & Slight 20 specImens 6 2.5 5.5
Below exposed in storage
liquid lank for 32 days
level (20 days in liquid
and 12 days in vaporl.
Corrosion
rales based on 20 days

100 510 950 I None Moderate 14

exposure in liquid
concentratIOn in
open pot !60 70 87 534 60 141

18
 PART III. CORROSION BY OTHER ALKALIES

caustic soda of similar concentration and tem-

A. Caustic Potash (KOH)
Caustic potash is produced by the electrolysis
of muriate (potassium chloride) brine. Several
types and concentrations of KOH are available,
but 45 and 50 per cent liquid and 85 and 90 per
cent solid are most commonly marketed. Above
about 50 per cent concentration, caustic potash
has a higher boiling point than caustic soda of
the same concentration. This differential is espe-
cially pronounced at high concentrations. For
this reason. the commercial product is usually not
concentrated above 90 per cent because of the
high temperatures involved.
In general. those materials which are useful in
caustic soda are also suitable for caustic potash.
Nickel 200 and INCONEL aHoy 600 are both suit-
able for service in hot caustic potash. as indicated
by the data presented in Table XXIII. Negligible
data exist for other nickel alloys in caustic potash.
Gegner has suggested that because caustic potash
is so similar to caustic soda. the corrosion data in
perature can be used to approximate corrosion
resistance in caustic potash. Iff
Under extreme conditions, some nickel alloys
are subject to stress-corrosion cracking in caustic
potash solutions. However, the information pre-
sented in Tables IX and X suggests that stress
corrosion cracking of Alloy 600, Alloy 400 and
Alloy K-500 is not quite as severe with caustic
potash as with caustic soda.
The beneficial effect of nickel in cast iron ex-
posed to caustic potash is shown in Table XXIV.
The reductions in corrosion rates are similar to
those obtained in caustic soda solutions.
Table XXV shows the results of laboratory cor-
rosion tests of several Ni-Resist alloys in hot. con-
centrated caustic potash. Lower corrosion rates
would be expected with a decrease in either tem-
perature or caustic potash concentration. Ni-
Resist Type 3 appears to have equivalent, and
sometimes superior. corrosion resistance in com-
parigon to Types 1 and 2.

Table XXIII
Corrosion Tests in Caustic Potash Solutions

Corrosion Rate. mils per year

KO"
COllcen- Temperature Test INCONEl. MONEl.
tration. Period. Nickel alloy aUoy
% C F Aeration Agitation days Comments 200 600 400

13 30 85 None due to 207 storage tank impurities- nil' nil nil

filling tank KJeo J 3 gpl. KCf 170 gpl.
KClO .. 0.1%
30 113 236 None Boiling 26 laboratory test-saturated l. 0.2 l. 0.1
with KCf. 0.05% KClO, V.0.3 V.O.1
47 139 281 None Boiling 26 laboratory test-saturated l. 0.1 l. 0.4
with KG\. 0.18% KClO, V.O.3 V.O.1
50 28 82 None due to 207 storage tank impurilies- nil nil nil
lilting lank K,CO. 0.3%. KGI 0.75%.
KGto, 0.10%
50 150 300 None 2\.61pm 7 laboratory test-U·Bend nil 0.5
specimen showed
. no cracking
50 150 300 None 3481pm' • 35 laboratory test nil 0.5
10 150 300 None 21.6fpm 7 laboratory test 0.4 0.7
10 150 300 None 3481pm" 35 laboratory test 1.6 5.7
• nil-less than 0.05 mils pel'" year. l-liQuid V-Vapor
." Specimens m~ved at th!s veloc11y fof'" 8 hr each working day and at zero ft per mtn overn1ght and duong
weekends. Th,s was equlvatent to ten 24 ·hour days at the high velocity rate.

19
 Table XX'V Considerable amounts of Types 316 and 316L
Effect of Nickel in Cast Iron stainless steels are used in the ammonia-soda
on Corrosion by Caustic Potash process for the production of soda ash (Na 2C0 3 ) .
Concentration: 950 g KOH per liter. The main reaction involves the carbonation of an
Temperature: 400 C (750 F). ammoniated brine to form sodium bicarbonate
and ammonium chloride. The ammonia is recov-
Nickel Content of Alloy Iron, Corrosion Rate,
% mils per year

o 21-30 Table XXVI

3 3.0
6.5 2.0 Plant Corrosion Test in Ammonia
12.4 0.4 Surge Vessel of Urea Manufacturing Plant
Solution: 22% NH, • 71 % H,O, 7% CO, and trace of
NH.NO, .
Temperature: 66C (150 F).
Test Period: 300 days.
Table XXV
Aeration: None.
Corrosion of Ni-Resists in Caustic Potash Agitation: Moderate.
Location: Uquid phase at bottom of aqua ammonia surge
Hi-Resist ClIrrosjon Rate, vessel.
Type Exposure mils per year
Corrosion Rate,
1 68-hour test in 81 % KOlt at 225 C (437 f) 30 Material mUs per year
2 68-hour test in 81% KOH at 225 C (437 f) 20
INCOlOY alloy 825 <0.1
3 68-hour test in 81 % KOH at 225 C (437 f) 10 Type 347 Stainless Steel <0.1
2 36-hour test in 92% KOlt at 268 C 1516 f) 10 Type 316 Stainless Steel <0.1
Type 304 Stainless Steet 0.3
3 3S-hour test in 92% KOlt at 268 C (516 f) 10 Type 316 Stainless Steel <Sensitized) 0.3
CARPENTER alloy 20 0.4
INCONEL alloy 600 3.4
Type 304 Stainless SteellSensitized) 7.6
Type 410 Stainless Steel Missing-presumed
B. Ammonia and corroded away
Mild Steel Missing-presumed
Ammonium Hydroxide corroded away
Most of the nickel-base alloys, with the exception
of the nickel-copper alloys and nickel itself, resist
all concentrations of ammonium hydroxide up to Table XXVII
the boiling point. Plant Corrosion Test in Mixed Ammonia-Carbon
Among the nickel-containing alloys, the aus- Dioxide Gas Stream in a Chemical Plant
tenitic stainless steels are most frequently em- Gas: Mixture of NHJ and CO2 with probably some moisture
present.
ployed in ammonia and ammonium hydroxide Temperature: 20 to SOC (68 to 176 F).
solutions. Austenitic stainless steels exhibit good Test Period: 68 days.
resistance to all concentrations of ammonia and Aeration: None.
ammonium hydroxide up to the boiling point. Agitation: Gas flow.
Tables XXVI through XXIX show the results of Location: Suspended in gas stream.
plant corrosion tests in ammonia- and ammonium Corrosion Rate,
hydroxide-containing process streams. Material mils per year
Stone .determined that Type 304 stainless steel, Type 304 Stainless Steet Nil·
which had been sensitized at 677 C (1250 F) for Type 316 Stainless Steel Nil·
one hour, was not subject to intergranular corro- MONEL alloy 400 2.2
tNCONEL alloy 600 3.0
sion during a 40-week exposure in 28% NH 4 0H
Mild Steel 5.1
at room temperature. 12 However, this resistance Nickel 200 5.3
does not extend to elevated temperatures in com- Silicon Bronze 72
mercial solutions, as shown in Table XXVI. • Nil == Less than 0.01 mill><" year.

20
 Table XXVIII Table XXX
Plant Corrosion Test in Ammonia-Carbon Plant Corrosion Test in Ammonia Recovery Still,
Dioxide Gas Stream in a Metal Refining Plant Ammonia-Soda Process for Production
of Sodium Carbonate
Gas: 26% NH J • 14% CO,. balance water vapor.
Temperatur-e: 66 ro 93 C (150 to 200 F); Average 82 C Middle Section
(l80 F). Temperature: 60 to 71 C (140 to 160 F).
Test Period: 65 days. Liquor Composition: 2% NH l , 9% NH.CI,
Aeration: Moderate. 14% NaCl, 2% CO2 •
Agitation; 25 to 40 fps gas flow. Test Period: 220 days.
Location: NH1·CO~ stripping still overhead line. Top Section

Corrosion Rate. Temperature: 60 to 71 C (140 to 160 F).

Material mils per year Liquor Composition: 5% NH l
• 9% NH.CI,
14% NaCl, 3.4% CO2 •
Type 202 Stainless Steel <0.1 Test Period: 220 days.
Type 304 Stainless Steel <0.1
Type 316 Stainless Steel <0.1 Corrosion Rate, mils per year
INCOlOY alloy 825 <0.1 Middle lop
INCOLOY alloy 800 1.5 Material Section Section
INCONEl alloy 600 4.1
Type 410 Stainless Steel 0.1 Type 316 Stainless Steel OJ 0.1
Type 502 Stainless Steel 20 Zirconium 0.1 0.1
Mild Steet 22 Titanium 0.1 0.2
HASTEllOY alloy C 0.1 14'
Nickel 200 >33" >32"
Mild Steet >73" >71"
Table XXIX
• Specimen pitted in crevice beneath insulating wasber.
Plant Corrosion Test in Contaminated •• Specimens cQrroded away..
Ammonia Vapors in a Coke By-Products Plant
Gas: Ammonia vapors plus H,S. CO,. HCN. phenols and Nickel is not attacked by anhydrous ammonia,
steam.
but is resistant to ammonium hydroxide solutions
Temperature: 100 to 110 C (212 to 230 F); Average 105 C
(221 F). in concentrations only up to about one per cent.
Test Period: 144 days. Aeration may induce passivity in concentrations
Aeration: None. under 10 per cent, but even in the presence of air,
Agitation: High velocity gas flow. more concentrated solutions are highly corrosive
location: Ammonia liquor still vapor outlet. to nickel. The corrosion data shown in Table XXXI
Corrosion Rate, were obtained in room-temperature laboratory
Material mils per year tests ()f 48-hour duration in one normal ammo-
Type 304 Stainless Steel KiI- nium hydroxide, following a previous 48-hour ex-
Type 316 Stainless Steel Nil'
I NCONEl alloy 600 0.1
Mild Steel S.O
MONEL alloy 400 >40 Table XXXI
(corroded away)
Nickel 200 >40 Corrosionof Nickel 200 in One Normal
(corroded away) Ammonium Hydroxide (1.7% NHa)
• Nil "" 1.ess tban 0.04 mils per year. Corrosion Rate,·
Test Condition milspllryear
ered in this process for reuse. Table XXX shows Total Immersion
corrosion rates for metals and alloys in an am- Quiet 0.8
monia recovery still in a soda ash plant. The pos- Air"'Agitated <0.1
sibility of pitting must be taken into account in Alternate Immersion
Conti!luous 2.7
the design of equipment where there are such lntermittent 0.4
high chloride levels, so as to avoid crevices where Spray {4 to 30 Daysl <0.1
chlorides can concentrate to even higher levels
• Specimens exposed at room temperature tor 2 days after a previous
and promote crevice corrosion. 2-day exposure except for spray expo'Sure.

21
posure. The re~ults of 20-hour tests in highly
agitated ammonium hydroxide solutions at room
tempel·ature are shown in Table XXXII. Typical
corrosion rates for Nickel 200 in several indus-
trial exposures are also given in Table3 XXVII,
XXIX and XXX.

Table XXXU
Corrosion of Nickel 200 in
Ammonium Hydroxide Solutions
NH.OH Cancentration, CCIfI"lISion Rate, •
% mils per year

1.1 o
12.9 560 Fig. 12 - Sodium carbonate filters use Type 304 stainless
20.2 370 steel or MONEL alloy 400 for the perforated backing sheet or
27.1 180 winding wire. The same materials are also used for back·
ing wire cloth and facing cloth .
• Tests run to agitated solution at room temperature for 20 hours.

salt solutions can be handled in the same materials

Nickel-copper alloys. such as Alloy 400, are re-
sistant to anhydrous ammonia and are slightly
more resistant than commercially pure nickel in
ammonium hydroxide solutions. as shown in Table
XXXIII. However, their usefulness is restricted
to dilute solutions up to about 3<1· ammonium
hydroxide. In solutions of higher concentration.
corrosion rates are increased considerably by
aeration and agitation.
TableXXXm
laboratory Corrosion Tests of
MONEL alloy 400 in Ammonium Hydroxide
Temperature: Room. Test Period: 20 hours.
Agitation: 371 feet per minute.
HH3 Cancentration,
% mils per year
2.7
3.6
5.5
8.2
11.1
18.3
25.8
suitable for caustic soda. As with caustic soda,
dilute solutions at low temperature are not very
corrosive to carbon steel and may even act as cor-
rosion inhibitors, but concentrated solutions at
high temperatures often require nickel or high
nickel alloys.
The results of tests within an evaporator han-
dling sodium metasilicate are shown in Table
XXXIV.
Another plant test in a kettle during the dis-
solving of silicates in strong caustic soda gave the
corrosion rates shown in Table XXXV.
The superiority of Alloy 400 and austenitic
stainless steels for a phosphate hydration was
demonstrated in a short-duration test shown in
Carrosian Rate, Table XXXVI.
Nickel and high nickel alloys offer good resist-
o ance to corrosion by sodium sulfide solutions. In
70
298
317
Table XXXIV
327 Corrosion Tests in Sodium Metasilicate
231
Composition: 50% sodium silicate. 50% sodium hydroxide.
36
Ave~age Temperature: HOC (230 F). Test Period: 6 weeks.

Corrosion Rate.
Material mils per year

C. Other Alkaline Solutions of Nickel 200 <0.1·

Sodium and Potassium Salts MONEL alloy 400 <0.1
INCONEL alloy 600 <0.1
Salts su~h as sodium sulfide. sodium carbonate, Hi-Resist Type 1 0.4
sodium silicates, trisodium phosphate and others Mild Steel 13
Cast Iron 18
form alkaline water solutions. These alkaline

22
 Table XXXV centrate sodium sulfide from 25 to 60 per cent
Corrosion Te.sts During Dissolving of are given in Tables XXXVIU and XXXIX. Oper-
Silicates in Caustic Soda ating experience over a number of years with
Location: Test specimens suspended near bottom of kettle. evaporator tubes in sodium sulfide evaporation
Temperature: 77 C (170 f). Test Period; 32 days. has shown that Nickel 200 and Alloy 400 are
COffoswn Rate,
satisfactory for this application.
Material mils per year Experience has also demonstrated that Alloy
Nickel 200 0.1
600 is useful .for direct-tired pans in which sodium
Ni:Resist Type 3 0.2 sulfide is eoncentrated from 25 per eent to 60 per
Ni:Resist Type 2 0.5 cent. Operating temperatures on the order of 150
Nickel Cast Iron (3% Ni) 8
Cast Iron
to 177 C (300 to 350 F) prevaiL Under sueh condi-
33
Mild Steel 41 tions. Alloy 600 has given a service life of up to
eight years.
Table XXXVI
Table XXXVIlI
Conosion Tests in Phosphate Hydrator
Plant Corrosion Test in Direct·Fired Open Pot Used
Composition: 50% solution of sodit.t1l1 tripolyphosphate and for Concentrating Sodium Sulfide to 60 Per Cent
sodit.tm tetrapotyphosphate.
Average Temperature: 74 C (165 F}. Test Period: 60 hours. Temperature: 100 to 180C (212 to 356 f).
Aeration: Extensive. Agitation: Considerable. Test Period: 81 days.

Corroswn Rate, Corrosion Rate.

Material mils pet year Material mils per year

Type 3114 Stainless Steel 0.1 MONEL altoy 400 8

Type 316 Stainless Steel 0:4 fMCOJltEl..alloy 600 10
MONEt. alloy 400 0.7 Nickel 200 16
Mild Steel 133 Copper-Nickel alloy CA 715 20
HASTELLOY alloy B 22
ILLiUM G 48
10:t sodium sulfide. the corrosion rates are quite Type 316 Stainless Steel >72*
Type 3114 Stainless Steel >73*
Jow. as shown in Table XXXVII. The most severe KASrELLOY alloy C >85*
service conditions are encountered in hot. concen- DURIMEr alloy 20 110
trated solutions. The results of two plant corro- ~ Specimens corroded away.
sion tests in direct-fired evaporators which con-
Table XXXIX
Table XXXVII
Plant Corrosion Test in Gas-fired
Plant Corrosion Test in a Open Tray Used for Concentrating
Sodium Sulfide Storage Tank Sodium Sulfide from 25 to 60 Per Cent
Solution: 10% Na 2 S. Aeration: Open tank. Temperature: 125to 175C (257 to 347 f).
Temperature: Atmospheric. Agitation: Only due to filling tank. Test Period: 19 days.
Test Period: 81 days.
Corroswn Rate.
Corrosiolt Rate. Material mils per year
Matl!rial mils per year
MONEL alloy 400 3
. Nickel lO!l <OJ Type 310 Stainless Steel 7
MQNEL alloy 400 <OJ Type 309 Stainless Steel 8
tNCONEL alloy 600 <OJ Nickel 200 11
KASrELLOY all.oy B <0.1 INcoNELa1loy 600 22
HAsrULOY atloy C <OJ Type 304 Stainless Steel 84
Type 304 Stainless Steel <0.1 Type 3D2 Stainless Steel 230
Type 316 Stainless Steel <0.1 Type 330 Stainless Steel >290*
ILLlUM G <fU Type 316 Stainless Steel >300'
DURIMEr 20 <0.1 Mild Steel >600*
Copper-Nickel alloy CA 715 1.3
• Spedmens corroded away.

23
 PART IV. INDUSTRIAL APPLICATIONS

A. Caustic Soda Manufacture equipment such as evaporators, heat exchanger

Service records, often dating back for 20 to 30
years, have demonstrated the satisfactory service
of nickel and nickel alloys in caustic soda manu-
facture. In one plant, nickel centrifugal pumps
handling 50% caustic soda from mercury cells are
27 years old and are still in operation. In another
plant, nickel evaporators continue to give good
service after 30 years' use. Nickel 200, low-car-
bon Nickel 201, Alloy 600, Alloy 400 and their
cast counterparts are "standard" materials of
construction, either solid or as a cladding for
tubing, pumps, crystallizers, valves, fittings, etc.,
used in the concentration and handling of caustic
soda. Corrosion test data cited earlier in this bul-
letin were obtained largely in caustic soda manu-
facturing processes.
A comparison of the corrosiveness of caustic
soda produced from mercury cells with that pro-
duced by diaphragm cells was made by Committee
T5A-3D of the National Association of Corrosion
Engineers. Data obtained in this survey are
shown in Table XL. It appears that there is not a

Fig. 13 - Triple-effect evaporators for the concentration of diaphragm cell liquor to 50% caustic soda_ All threeevapora-
tors are constructed entirely of Nickel 200 and Nickel 200-clad steel.
Photograph courtesy of Blaw-Knox Company_

24
 Table Xl
"Round Robin" Test Program by Four Caustic Soda Producers-Comparison of
Corrosiveness of Diaphragm Cell vs. Mercury Cell Caustic-
Conducted by NACE Committee TSA-3D
Average Temperature
Corrosion Rate.
Company mils per year
1 2 3 4 C.Dmpany
Material Corredent C f C f C F C F 1 2 3 4
Nickel 200 50% NaOH-Oiaphragm Cell 35 95 29 85 88 190 54 130 <0_1 <0.1 <0.1 <OJ
Hickel 200
Hickel 200
50% NaaH·t>iaphragm Cell 40 104 - - - - Ambient
60 140
<0.1 <0.1
50% NaOH·Mercury Ceil 38 100 105 221 82 180 <0'\ <0'\ 1.0 <0.1
Nickel 200 50% NaOH·Mercury Cell 37 98 45 113 - - Ambient <0.1 <0.1 <0.1
Nickel 20:0 50% NaOH·Mercury Cell - - Ambient - - Ambient <0J <0.1
Nickel 20:0 73% NaOMHapluagm Cell 119 246 - - 99 210 - - <0.1
--
0.2
Nickel 200 73% NaOH-Oiaphragm Cell 125 257 - - - - - - 0.2
Nickel 200 73~4 NaOH·Mercury Cell 114236 - - - - - - 0.3
INCONEL alloy tioo: 50% NaOK-Diaphragm Cell 35 95 29 85 88 190 54 130 <0.1 (l) <0.1 <0.1 <0.1
INCONEL alloy 601} 50% HaOM·Diaphragm Cel! 40 104 - - - - Ambient <0.1 <0.1
INCONEL alloy 600 50% NaOH·Mercury Cell 38 100 105 221 82 180 60 140 <0J <0.1 <0.1 <OJ
INCONEL alloy 600 50~{' NaOH·Mercury Cell 37 98 45 113 - - Ambient <O.! <0.\ <0.1
INCONEl alley 600 50~{' NaOH-Mercury Cell - - Ambient - - Ambient <0.1 <0.1
INCONEL alley 600
INCONEl alloy 6{}0
73% NaOH-Diaphragm Cell
73% NaOH·Diaphragm Cell
119
125
246
257
- -
- -
99210
- -
-- -
-
<0.1
0.3
0.2

INCONEL alley 600:

MONEL alloy 400:

73% NaOH·Mercury Cell
50% NaOH·Oiaphraglll Cen
114 236 - - - - - - 0.2
35 95 29 85 88190 54 130 <0.1 <0.1 <0.1 <0.1
MONR alloy 400 50% N~OH'Diaphragm Cell 40 104 - - - -
Ambient <OJ <0.1
MONEL aliDY 41111 50% NaOH;Mercury Cell 38 100 105 221 82180 60140 <OJ 0.1 0.2 <0.1
MONEL aUoy 400
MONEL alloy 400
50% NaOH·Mercury Cell
50% NaOH-Mercury Cell
37
- -
98 45 113
Ambient
-
-
-
Ambient
-
Ambient
<O.} <0J
<0.1
<0.1
<0.1
MONEL alloy 400 73°kNaoH·Olaphraglll Cell 119246 - -,...,... - -
99 210 <0.1 0.8
MONEL alley 400
MONEL aUoy 400
73% NaOH-Diaphraglll Cell
13% HIlOa·Mercury Cell
125.257.
114236
-
- - - - - -
- ,.... - - 0.4
0.5
INCOLOY alloy 800 50% NIlOH·Oiaphragm Cell 35 95 29 85 88 190. 54130 <OJ <0.1 <0.1 <0.1
INCOLOY alloy 800
INCOLOY alloy 800
50%: HIlOH·tliaphragm Cell
50% NaOH·Mercury Celt
40 104
38100
-
105 221
- - - Ambient
82180 60 140
<IU
<0.1 «l.l <OJ
<0.1
<OJ
INCOLOY alloy 800 5{)%NaOH.Mercury Cell 37 98 45 113 - Ambient <0.1 <0.1 <0.1
INCOLOY alloy 800
IHCOLOY alloy 800
50~i. NaOH.Mercury Cell
73% NaOIH)iaphragm Cell
- -
119246
Ambient
- -
-
99.210
- Ambienl
- - OJ
<0.1
4..l (2)
<OJ

IHCOLOY alloy 800 73% NaOH-Diaphragm Cell 125251 - - - - - - 0.5

INCOLOY alloy 800

CARPENfER alloy 20 Cb·3

73% NaoN·Mercury Cell
50'!';' NaOH·Diaphragm Cell
U4.236
35 95
-29 -85 -
88 190
~
-
54 130
O.3IU
<0.1 <0.1 <0.1 <0.1
CARPEtffER alloy 20 Cb-3
CARPENfER alloy 20 Cb·3
50'!" NaOH·Oiaphragm Cell 40 104 - - - - Ambient <0.1 <0.1
<0.1
50% NaOK-Mercury Cell 38100 82 1811
105 221 60 140 <(j.l <OJ <0.1
CAftPEtffER alloy 20 Cb~
CARPENTER alloy 20 Ch·3
50% NaOH,Mercury Cell
50% NaON-Mercury Cell
37 98.
- -
45.113
Ambient
-- ~

-
Ambient
Ambient
<0.1 <OJ
<OJ
<0.1
<0.1
CARPENTER allDY 20 (:b·3 73% NaOH·Oiapllragm Cell U9246 - - 210 - - 0.4 1.5(3)
CARPENTER alley 20 tb·3
CARPENTER alllly20 (:b·3
73% NaOH·Oiilplnagm Cell
73% NaOH·Mercury Cell
125 257
H4236
- - - -
-- - - - -
- - 0.5
0.4
ACI tN-7M 50% NaOH·Oiaphragm Cell 35 95 29" 85 8'8 190 54130 <0.1 <0.1 <0.1 <0.1
ACt CN·7M 50% NaOH·Diaphragm Cell 40 104 - - - - Ambient <0.\ <OJ
ACI CtOM 50?{. NaOH·Mer(;ury Cell 38 100 105 221 82 180 60 140 <0.1 <0.1 <0.1 <0.1
ACl eN·7M - 50°4 NaOH·Men:ury Cell 37 98 45 il3 - - Ambient <0.1 <OJ <0.1
ACt CN-1M 50% NaOH·MeJ.eury Cell - - Ambient - - Ambient <0.1 <0.1
ACI CN-1M 73'l~NaOH-Dlaplmlgm Cell 119 246 - - 99210 - - lU 9.3
ACI CN-7M 73'}~ NlIOH,OillPhraCm Cell 125 257 - - - - - - 1.2 (J)
ACI CN"7M 13% NaOH.MetClifY Cell 114 236 - - - - - -' G.4
Ni·Re.sist Type 3 50% NaOH·Diapbragm Cell 35 95 29 85 88 190 54 130 0.2 <0.1 0.4 (4) <0.1
Ni-Resist Type 3 50% NaOH·Diaphragm Cell 40 104 - - - - Ambient 0.6 0.2
Hi-Resist Type 3 50% NaOH·Mercury Cell 38 100 105 221 82 180 60 140 <0.1 <0.1 <0.1 <01
 Table XL (Cont'd.)
"Round Robin" Test Program by Four Caustic Soda Producers-Comparison of
Corrosiveness of Diaphragm Cell vs. Mercury Cell Caustic-
Conducted by NACE Committee T5A-3D
Average Tempe,ature
Corrosion Rate.
Company mils per year
2 3 4 Company
Material Corrodent C f C f C f C f 1 2 3 4

Hi·Resist Type 3 50% NaOM.Mercury Cell 37 98 45 113 - - Ambient 0.2 0.1 0.1
Ni:Resist Type 3 50% NaOJ1,Mercury Cell - - Ambient -99 2W
- Ambient <0.1 0.2
Ni:Resist Type 3 73% NaOH-Oiaphragm Cell 119 241> - - - - 0.3 8.4
Hi:Resist Type 3
Hi:Resist Type 3
73% NaOM-Diaphragm Cell
73% NaOH·Mercury Cell
125 257
114 236
-
-
-
-
- -
- -
- -
- -
2.3
1.2
Type 3.16 Stainless Steel 50% NaOH~iapllragm Cell 35 95 29 85 88 190 54 130 <0.1 <0.1 3.3 <0.1
Type 3Ui Stainless Steel 50% NaOH~iaphragm Cell 40 104 - - - - Ambient 0.2 <0.1
Type 316 Stainless Steel 50% NaOH·Mercury Cell 38 100 105 221 82 180 60 140 <0.1 <0.1 0.2 <0.1
Type 316 Stainless Steel 50% NaOH·MercuI}' Celt 31 98 45 113 - - Ambient <0.1 0.1 0.3
Type 316 Stainless .Steet 5~% NaOH·Mercury Cell - - Ambient - - Ambient <0.1 <0.1
Type 316 Stainless Steel 73% NaOH~.iapllragm Cell 119 246 - - 99 210 - - 6 (4) 8.7
Type 3l6.stainless Steet 13% NaOH-Oiapbragm Cell 125 257 - - - - - - 13.1(5)
Type :116 Stainless Steel 13% NaOH'Mercury Cell 114236 - -. -
- - - 10 {4}
Type 304 Stainless Steel 50% NaOH·Diapllragm Cell 35 95 29 85 88190 54 130 <0.1 <0.1 1.1 <0.1
Type 304Stainle$$.Sieei 50% NaOlH)iallhragm Cell 40 104 - - - - Ambient <0.1 <0.1
Type ~04 Stainle$~ Steel 50% NaOn-Mercury Cell 38 100 105 221 82 180 .60 140 <0.1 0.1 n. 61 0.3 <0.1
11.0
Type 304 Stainless Steel 50% NaOH·Mercury Cell 37 98 45 113 - - Ambient <0.1 <0.1 0.4
1ype304 StaiRtessSteel 50% NaGH.Mercury Cell - - Ambient -99 210
- Ambient <OJ <0.1
Type 304 Stainles$.steel
Type 304 Stainless Steel
73~ NaOH-Oiapbragm Cell
73% NaOH-Oiaphragm Cell
119246
125 257
-
- -
- - -
- -
- -
15 (4)
19.4 t5}
13 m
Type 304 Stainless Steel 73% NaOH·Mercury Cell 114 236 - - - - - - 15 (4)
Ductile Cast Iren 50% NaOll·Diaphragm Celt 35 95 29 85 88 190 54130 1.4 3.1 12 2.6
Ductile Cast Iron
Ductile Cast Iron
50% NaOli-Diaphragm Cell 40 104 - - - - Ambient l.5!S)
0.6
52
1.0
50% NaOH·Mercury Cell 38 100 105 221 82 180 60 140 0.4 0.3
Dllctil~cast Iron 50% NaOli·Mercury Ce:t 37 98 45113 - - Ambient 1.8 2 (81 6.2(2
Ductile Cast IllIn 50% NaOJt..Men:l.lry tet! - - Ambient - - Ambient 3.7 2.6
D1Ictile Cast Iren 73% NaOH~iapllfagm Cell 119246 - - 99 210 - -
- -
73 18
Ductile Cast illln 73% NaOH~iaph[agm Celt 125 251 - - - - 106
Ductile cast Iron 13% NaOH.MercuI)' Celt 114236 - - - - - - 103
Gray Cast Iron 50% NaOH-Oiaphragm Cell 35 95 29 85 88 190 54 130 2.1 1.9 13 2.9
Gray Cast Iroll
Gray Cast Iron
50% Na(lli-Diaphragm Cell
50% NaQli-Mercury Cell
40
38
104
100
-
105 221
- - -
82 100
Ambi'lnt
60140
1.9
0.4 2 t9) 2.6
7.9
1.7
Gray Cast Iron 50% NaOH·Mercury Cell 31 98 45 113 - - Ambient 2.1 3 5.1
Gray Cast Iron 50% NaOli-Mercury Cell - - Ambient -99 2It}
- Ambient 4.5 3.5
Gray Cast Iron 73% NaOli-Dia.phragm CeU H9246 - - - - 54 21
Gray Cast Iron 73% NaOn-Diaphragm Cell 125 257 - -- -- -- - -- 44
Gray Cast Iron 73% NaOK-MereuI}' Cell 114 236 - - 82
MildSteeJ 50% HaOH-Oiapbragm Cell 35 95 29 85 88 190 54130 UJ5} 1.4 nO} 20 2.1
Mild Steel
Mild Steel
50% NaOH~iallhragmCeIi
50% NaOH·Mercury Cell
4D 104
38 100
-
105 221
- - 82 180
- Iynbient
60 140
1.5 (5)
O.SISI 3 {6.1ID 1.8m
3.2
1.2
21
Mild Steel 50% NaOH·Mercury Cell 37 98 45 113 - - Ambient 1.4 2 2.9(5
Mild Steel - 50% NaOM-Mercury Cell - - Ambient - - Ambient 5.1 1.9
Mild Steel 13% NaOH·l)iapilragm Cell 119 246 - - 99210 - - 59 5.7
Mild Steel 73% NaOfl..Diapbragm Cell 125 251 - - - - - - dissolved
>38
Mild Steel 73% NaOM·Mercury Cell 114 236 - - - - - - 71
(1) Pitted to a maximum dept" Qt 1 mHo (5) Pitted to a ma.ximlJm depth Qt 3 mils. (1) Pitted to a maximum depth of 8 mils.
(2) Pitted to a maximum depth of 4 mils. (6) Mercury droplets in tao". 2 rates shown (8) Pitted to a maximum depth of 2 milS.
(3) Pitted t<> a maximum depth of 5 mils. are for the duplicate speCimens (9) Pitted to a maximum depth of 12 mils.
(not averaged): specimen with high rate
(4) Stress-corrosion crack through (10) Pitted to " maximum depth of 11 mils.
showed stress-acce1erated local attack.
one of the identifying punch marks.

26
great deal of difference in the corrosiveness of the rates. Some corrosion test data showing the ef-
caustic produced by these two types of cells, al,'ld fects of chlor;;ltes upon the corrosion of Nickel 200
that other variables such as temperature and con- and INCONEL alloy 600 in high temperature caus-
centration are more important in influencing cor- tic soda are shown in Tables XLI and XLII. There
rosion rates. are several means by which chlorates can be re-
Prior to about 1946, the concentration of 50%
or 73 % caustic soda to anhydrous was carried out Table XU
entirely in direct-tired caustic pots in a batch Plant Corrosion Test During Concentration of
operation. These pots Were usually constructed of Diaphragm Cell Caustic Soda from
gray cast iron. Nicl<:el could not be used because 50 Per Cent to Anhydrous
of the practice of "sulfur shading" (sulfur addi- Feed liquor c.ontained 0.24% scdium chl.orate and 1.0%
scdium chloride .on S.olid caustic basis. Rapid circulation
tion for the removal of iron and other contamin- of liqu.or.
ants to achieve higher purity and better product Temperature: 400 C (750 fl.
color), which caused severe sulfur embritllement Test Period: 243 hcurs .operaticn.
of the nickel at the high temperatures involved. Corrosion Rate. mils per year
Subsequent to 1946, these pots have been Material liquid Vapor
repla<:ed to a very great extent by nicl<:el and
nickel anoy equipment for continuous vacuum Hickel 2DD 51.0 0.5
tHCONEt. anoy 6IJD 87.0 5.0
evaporation, which has proven to yield a higher
quality product more economically.3.20 The pro-
duction of anhydrous caustic soda in corrosion- TableXUl
resistant Nickel 201 and AHoy 600 equipment has laboratory Corrosion Test in Evaporation
eliminated the necessity of sulfur shading. of Caustic Soda from 73 tQ 96 Per Cent
with and without Chlorate
Temperature: 180 C (360 F) t.o 450 C (840 F).
lest Pericd: 24 h.ours.
Corrosion Rate, mils pef year
Without Witll fl.3% Clllorate
Material Chlorate (Solid C;tIIStic Basis)

Nickel 2IltJ 1.5 260

IHCOHEt. alloy 6flO 2.2 380

moved; the addition of sucrose (U. S. Patent

fig. 14 --Evaporator bodies and vapor piping at a large
chlorine-caustic soda plant for concentraticn t.o 730/0 NaOH.
All evaporatcrs are constructed entirely .of Nickel 200 and
Nickel 200·clad steel.
Chlorates are removed from diaphragm cell
caustic soda when concentrating to anhydrous in
nickel or high nickel alloys to minimize corrosion
2,610,105) or dextrin (British Patent 778.226)
appear to be the most common. While these ad-
ditions minimize corrosion and attendant metal
contamination of the product,- they do increase
the carbonate concentration. Bradbury and
Cooper have shown that the addition of sorbitol
and subsequent heating will also remove chlo-
rates but with the formation of less carbonate.21
Liquid-liquid extraction with ammonia is also
widely used to remove chlorates and chlorides.22
In the continuous vacuum concentration and
production of anhydrous caustic soda, low-carbon
Nickel 201 and Nickel 201-clad steel equipment
have given excellent service as evaporator tubes.
tube sheets and shells, and as receiving tanks and
piping.

27
 Alloy 600 has also been used extensively for
producing anhydrous caustic soda and is the
preferred material of construction where the
heating is accomplished with any media in which
there is a po:.;sibility of sulfur compounds being
present. Alloy 600 for this service should be
stress-relieved or annealed as indicated in the dis-
cussion of nickel-chromium alloys in Part II of
this bulletin.
caustic potash at concentratiolls of 90 per cent
and above.
C. Caustic Soda Storage and
Transportation
After extreme care has been taken to assure
high purity in the production of caustic. it is
important that storage and transportation facili-
ties provide for continuing product purity. NickeI-
clad steel tank cars have been used for transport-
ing iron-free caustic since 1930. Nickel and nickel-
clad steel barrels are also in use for the transpor-
tation of smaller quantities. More recently. nickel-
plated steel tank cars and piping have been
employed.
The first tank-trailer constructed of INCOLOY
alloy 825 was put in service in 1963 to haul 50%
caustic soda. This alloy was selected because of its
versatility in its ability to transport other corro-
sive materials induding sulfuric. nitric and phos-
phoric acids. INCONEL aHoy 600 was selected for
barge tanks to carry 73 (-; caustic one way and
return with ammonia-base fertilizers or jet fueL

Fig. 15 - Tubes fabricated from Nickel 200 afe used in the

inclined heat exchanger in front of the Nickel 200-dad
evaporator which prodl.l<.:es 50% caustic soda.
separator atop the system. which separates
sodium chloride and other salts from the caustic solution.
is also Nickel 200.

B.Caustic Potash Manufacture

The production of caustic potash is carried out
in nickel and nickel alloy equipment in a similar
manner t9 the production of caustic soda. One
important difference. however, is the higher
boiling point encountered in caustic potash above
50 per cent concentration. Because of the higher
temperahx ~~; involved. cathodic protection is
often used for low-carbon Nickel 201 or high Fig. 16 - Marine terminal where caustic soda is unloaded
from barge. Nickel 200 lined caustic transfer pipe is at right
nickel alloy equipment u:=;ed for the production of foreground.

28
 Tt'an;;fer of materia! to and from storage tanks
usually requires pumps. Table XLIII shovv's the
results of a plant test in which Xickel 200, MONEL
alloy 400 and INCONEL alloy 600 corrosion coupons
wet'e subject to turbulent flow just downstream of
a pump handling 50('~ caustic soda. Similar cor-
rosion resistance would be expected fl'O!1l the cast
counterparts of these wrought materials (ACI
CZ-IOO, M-35 and CY-40). Pumps cast from ACI
CZ-IOOhave given over 25 years service as previ-
ollsly noted.

Table XLIII
fig. 17 ~ This barge carries 50%. caustic soda from a
field Test in 50% Caustic Soda mercury cell plant to storage facilities'along the Tennessee.
Just Downstream of a Pump Ohio and Mi Rivers. Four cylindrical tanks have a
total capacit liquid tons. To insure a long sef\lice
Temperature: 60 to 70 C (140 to 158 f); life for the ge and to protect product purity. all cargo
AI/erage 65 C (149 f). piping is either solid Nickel 200 or Nickel 2oo-clad steel with
Test Period: 393 days. Nickel 200 fittings: The cargo fromal! four tanks empties
into a Ni,ckeI2oo-clad steel well from which ,it ispl.lmped to
Aeration: Moderate. on-shore facilities_' .' . '
flow; 100 gpm in 3·inch pipe.

Corrosion Rate.
Material mils per year The use of nickel;..cla<i steel .tanks offers par-
Nidle1200 a.OJ ticularj\dvantage.<; in the storage and shipment
lNCON~L alloy 600 0.03 of 13~ caustic soda. To a\'Qid solidification;caus-
MONEL aUoy 400 0.10 tic of. this st~ngth must be loaded hot and main-

_ ..

fig. J,8 -:- INCOLOY aUoy 8,25 ,is used for the inner tank and all internal parts that come into contact with corrosil/e cargoes
in these two trailers-inner shell and heads. manhole ring and cover. dip tubes. spill dam and discharge pipe. Although
presently used for hauling 50% caustic soda. the corrosion resistance of this material will allow the hauling of a variety of
corrosives.
tained above the freezing point. Tables XLIV and D. Soap Manufacture
XLV give the results of tests in transportation Soaps are made by the reaction, called "saponi-
and storage facilities. fication,"between alkali and fatty oils (gly_
It is common practice to load and unload cars cerides) and fatty acids of animal or vegetable
of 73% caustic through Nickel 200 heat exhang- origin, or a mixture of both. The largest produc-
ers, pumps and piping. tion, and the most familiar, is "hard" soap made
with caustic soda as the saponifier. Caustic potash
Table XLIV produces a "soft" or liquid soap.
Field Test in Tank Car Transporting In certain high grade soaps, it is necessary to
74% Caustic Soda avoid contamination by such metals as iron and
Temperature: 130 C (265 F). copper in order to obtain a high quality product.
Test Period: 11 trips of 7·9 days. Therefore, pure caustic must be used in combina-
Aeration: None. Agitation: By movement of tank cars. tion with corrosion-resistant equipment. The
Corrosion Rate, matter of iron contamination is particularly sig-
Material mils per year nificant in soap-boiling kettles because the soap
Nit;lle1200 0.3 spends so much time there. particularly in the fuH-
INCOlOY alloy 825 0.3 boiled process. This is especially significant in the
MONEL alloy 400 0.4 upper parts of the kettles where corrosion rates
CARPENTER alloy 20 0.9
Type 316 Stainless Steel 8.4 are highest. Table XLVI shows the results of one
plant corrosion test in a soap-boiling kettle. Some
of the earliest applications of ~orrosion-resistant
materials were in the construction of soap kettles.

Table XLVI
Plant Corrosion Test in Soap·Boiling Kettle
Specimens immersed near the top of the settling cone duro
ing saponification and graining.
Temperature: 70 to 100 C (160 to 212 F).
Test Period: 106 days.

Corrosion Rate.
Material mils per year

Hit;ke1200 <0.1
Fig. 19 - 1300 feet of transfer pipe with a rolled and MONEL alloy 400 <0.1
welded internal lining of Nicke1 200 carries 50% caustic .NCOffEl. alley 600
soda from a marine terminal to a Nickel 2oo·c1ad storage <0.1
tank. Nickel 200-clad tank cars are in the background. Hi·Resist Type 1 0.1
Mild Steel 3.2
Cast Iron 11.0
Table XLV
Field Test in Storage Tank for 73% Caustic Soda
The first step. in most cases, was to line the upper
Temperature: 116 C (240 F). portions of existing steel kettles with Nickel 200.
Test Period: 183 days.
AHoy 400 or either Type 304 or Type 316 stain-
Aeration: None. Agitation: None except for filling of tank.
less steel. Because of occasional difficulties win
Corrosion Rate, these lined vessels (usually weld cracks in thE
-Material mils per year
liner because of differential thermal expansior
Nickel 200 0.3 between the steel kettle and the liner) , new vessel:
I NCONEl alloy 600 0.4
MONEL alloy 400 0.7
were sometimes constructed completely from cla(
Zirconium L4 plate. The same materials are also used for heat
Titanium 4.7 ing coils. swing pipe, kettle covers and othe
Mild Steel Destroyed during test
accessory equipment.

30
 Much of the corrosion test work in soap plants
has been concerned with the treatment of spent
soap lye and recovery of glycerine. since these
processes represent particularly corrosive condi-
tions. The pH of the solution during acid treat-
ment is usually 4 to 4.5 and sometimes as low as
3, due to the presence of hydrochloric or sulfuric
acids. Agitation of the mixture with air, a com-
mon practice, tends to increase the corrosion rate
of steel. The results of six tests during acid treat-
ment in four different soap plants are shown in
Table XLVII.
Alloy 400 and Nickel 200 or steel clad with
these materials are used for both acid-treating
and caustic-treating tanks because of their resist-
ance in both environments. Austenitic chromium-
nickel stainless steel and Alloy 600 are also used
but pitting is possible with these alloys under
certain conditions as shown in Table XLVII. Ni-
Resist Type 3 is used instead of Types 1 or 2 for

Table XLVII
Plant Corrosion Tests in Acid Treatment of Spent Soap lye
Test 1: Immersed in acid treating tank in mixture of 13% NaCI and 4.5% glycerine to which
is added 150 Ib of 28% HCI and 75 Ib of 17% aluminum sulfate per 30,000 Ib soap
lye. Temperature: 1 to 82 C (30 to 180 F). Test Period: 167 days. Plant L
Test 2: Immersed half·way down in acid treating tank in mixture of 18% NaCI plus glyce.rine
to which is added 0.5% solution of aluminum chloride. Aerated. Average tempera·
ture: 74 C (160 F). Test Period: 65 days. Plant 2.
Test 3: Immersed in trough of filter in acid treated filtrate from Test 2. Aerated. Average
temperature: 71 C (160 F}. Test Period: 65 days. Plant 2.
Test 4: Immersed half·way down in acid·treating tank in mixture of 8 to 10% NaCI and 4.5%
glycerine made acid to pH 4.5 with HCI and ferric chloride. Air agitation. Temperature:
21 to 71 C (70 to 160 F). Test period: 28 days. Plant 3.
Test 5: In acid treating tank in spent soap lye made acid to pH 4.5 with HCI and ferric chlo·
ride, and aluminum sulfate. Agitated wiUl1iIir. Temperature: 54 to 79 C (130 to 114 F).
Test Period: 45 days. Plant 3.
a. Immersed in bottom of tank near air inlet.
b. In vapor in top of tank. .
Test 6: Immersed half·way down in solution containing 13 to .16% NaCI plus Na2S0. and
10 to 12% glycerine made acid to pH 4.5 with sulfuric acid and ferric chloride.
Aerated. Temperature: 32 to 100 C (90 to 212 fl. Average 85 C (180 Fl. Test Period:
105 days. P\ant4.

C.onosion llate.lIllJs per year

Test 1 Test 2 Test 3 . TesH Test Sa Test Sh TestS
Material Plant 1 Plant 2 Plant! Plant 3 Plal1t3 Plant 3 fitaltt4

MOHEL alloy 400 .9 0.3 4.8 2.9 5.6 4.4 16.0

Hickel 200 1.1 0.9 3.7 L8 5.1 4.7 10.0

IHCOHEL aUoy SOO .6 <.1 .7 0.8 .7

Type 302 stainless steel <.1 .7 (a) O.5!d

Type 304 stainless steel .5!d LOlh)

Type 316 stainless steel <.1 A (b) LO(i)

Copper·Nickel alloy CA 715 27.0

Aluminum. Type 1100 4.4 (d)

Hi·Resist Type 3 3.0

Hi· Resist Type 2 2.7 1.0 4.0
Hi·Resist Type 1 2.5 0.9 3.4 5.0
Mild Steel 5.3 3.0 17.0 16.0 29.0 (e) 34.0(gl 14.0
Wrought Iron 18.0 24.0 (f) 44.01gl 14.0
Cast Iron 11.0 6.0 16.0 14.0
(a) Perlorated by pitting. original thickness 31 mils. (f) Pitted to maximum depth of 9 milS.
(bl Pitted to maximum depth of 11 mils. (gl Pitted to maximum depth of 8 mils.
(e) Pitted to maximum depth of 5 mils. (h) Pitted to maximum depth of 6 mils.
(d) Pitted to maximum depth of 3 milS. (i) Pitted to maximum depth of 14 mils.
(e) Pitted to maximum depth of 20 mils.

31
the construction of soap lye filters and filter plates tered in a lye tank and a centrifuge in one of these
to withstand possible therma·' shock when the hot processes.
solutions enter a cold filter process. Pumps of
iron-base nickel-chromium-copper-molybdenum Table XLIX
alloys such as WORTHITE or DURIMET 20 have given Plant Corrosion Test in Third-Stage Centrifuge
good performance handling both acid- and Specimens located at soap discharge. Mixture contained
alkali-treated soap lye. Austenitic chromium- 15% NaOH and 11 % NaC!. Low aeration, flow 350 gallons
per hour through 4·inch pipe. .
nickel stainless steels, usually Type 304, have been Temperature: 91 to 96 C (195 to 205 F).
used to advantage for "finishing and packaging" Test Period: 102 days.
equipment.
Corrusion Rate, Maximum Depth
Although a considerable amount of the world's Material mils pef year of Pitting, mils
soap is still produced batch-wise, efforts to reduce
Nickel ZOO Nil o None
the 4 to 11 days required with the fun-boiled kettle MONEL alloy 400 Nil None
method have resulted in a number of continuous I/'ICONE.L alloy 600 Nil None
processes for soap manufacture. In one such Type 304 Stainless Steel 0.1 None
Type 316 Stainless Steel 0.1 None
process, blended fats with zinc oxide catalyst are Type 341 Stainless Steel 0.1 None
reacted countercurrently with water in a 65-foot- Hi-Resist Type 1 0.4 None
high. Type 316 stainless steel hydrolyzing tower Mild Steel 10 Perforated
maintained at 282 to 260 C (450 to 5(,)0 F) and Cast Iron 12 55

600-700 psi. Fatty acids are continuously drawn • Less than 0.05 mils per year.

off the top and crude glycerol off the bottom of the
column. The fatty acids arevacuum-distiUed and
then neutraiized in a high-speed mixer· with a
caustic soda solution containing salt. thus produc-
ing soap in about four hours.24
In other continuous processes which usually
utilize centrifuges. the corrosives encountered
are much the same and considerable quantities of
austenitic chromium-nickel stainless steel. Alloy
400 and Nickel 200 are utilized. Tables XLVIII
and XLIX indicate the corrosion rates eneoun-
Table XLVIII
Plant Corrosion Testinfourth·Stage lye Tank
Immersed in tank containing soap lye with
11% MaC!..
Temperature: 88 to 96C (190 to 205 F).
Test Period: 102 days.
Corrosion Rate,
Material mils per year
E. Pulp and Paper Industry
Over a million tons of caustic soda are used
annually in the pulp and paper industry, prin-
cipally for the extraction of alkali-soluble impuri-
ties in multistage bleaching and for pH control.
Small amounts are used for preimpregnation of
wood chips and for the production of soda pulp.
More than two-thirds of aU paper is pX'Qduced
by the Kraft process. Digestion of certain soluble
portions of wood chips is accomplished by a hot
alkaline liquor consisting of a mixture of dilute
caustic soda and sodium sulfide with a total alka-
2% MaOH and linity of about 3 per cent. The following are prin-
cipal areas where carbon steel may corrode at
an excessive rate and nickel-containing alloys
(usually austenitic chromium-nickel stainless
Maximum Depth steels) can be used to advantage.
of Pitting, mils

Nickel zno Nil o None 1. Digesters

MONEL alloy 400 Nil None
INcolfEl aUoy 600 Nit None Batch-type Kraft digesters are commonly built
Type 316 Stainless Steel Nil None of carbon steel with a corrosion allowance in
Type 341 Stainless Steel Nil None excess of one inch. Until recent years this resulted
Type 304 Stainless Steel 0.1 None
Hi·Resist Type 1 0.1 None
in a service life of about 15 years, but with the
Mild Steel 1.0 7 increasingly severe conditions imposed. by modern
Cast Iron 3.0 22 pulping methods, service life was reduced to about
• Less than 0.05 mils pel' year. 7 to 9 years. Weld overlays employing AWS E310,

32
or A WS E310-Mo. have been employed to extend Table LI
the service life of corroded steel batch digesters. Plant Corrosion Test in a Digester Utilizing
Table L indicates the excellent corrosion resist- a Duplex Sulfate Process
ance of stainless steel and several other nickel Temperature: 100 to 171 C (212 to 340 f).
alloys in one Kraft digester. Cycle: Chips steamed for one hour, temperature rises from
100 C to 118 C (212 to 244 f). Acid liquor removed.
Alkaline liquor containing 82 gpl NaOH and 25 gpl
Na,S added. Charge brought to 171 C (340 f). cooked
Table l for total of 5 hours.
location: In vapor. Test Period: 731 days.
Plant Corrosion Test in a Sulfate Process,
Alkaline, Wood Pulp Digester Corrosion Rate,
Material mils per year
Temperature: 177 C (350 f).
Test Period: 586 days. Type. 316 Stainless Steel 0.1
Aeration: None. Type 341 Stainless Steel 0.1
Agitation: Violent boiling during cook. CARPENTER alloy 20 0.1
Top--Vapors in the top of the digester. Occa· INCj)NELalloy Spo OJ
sional splashing of chips, pulp and cooking MONEL alloy 400 23
liquors. Titanium 55
Bottom-Liquid and slurry on bottom screen of Mild Steel 107
digester.
Specime(ls: Combination of stress and general COrrosion.
Strips were stressed beyond the yield point by
bolting down over a fulcrum. Some specimens
were welded or contained weld overlays as
noted. No stress· corrosion cracking occurred.

Corrosion Rate,
mils per year
Material Condition Top Bottom
INCONEL alloy 600 Plate. as·received 0.02 0.21
CARPENT£R alloy 20 Welded 0.03 0.09
INCoNEL alloy 600 Welded 0.03 0.23
INCOlOY alloy 825 Plat.e. as·received 0.03 0.09
INCOlOY alloy 825 Welded 0.03
Type 316 Stainless Steel Plate, as·received 0.04 0.15
Type 316t. StainJess steel Plate. as·received 0.05
Type 31Sl Stainless Steef Welded 0.06 0.17
Type 316 Stainless Steel Welded 0.06 0.15
AViS Eltflllveriay on Steel Weld Overlay 0.05 0.17
Note: A dash indicates no coupon was exposed.

There are a few Kraft digesters that utilize a

duplex process in which the charge is initially acid
(pH 4) and later alkaline. Table LI shows corro-
sion rates in this process.
There are several hundred continuous digesters
operating on wood chips in the United States.
Fig. 20 ~ This top separator on a KAMYR continuous di·
These are constructed primarily from carbon gester separates the chips from the flushing liquor. With the
steel with high corrosion rate areas lined or clad exception of the drive mechanism. this separator is can·
structed of Type 304 stainless steel.
with Type 316L stainless steeL These high corro-
sion rate areas include the upper section. where
fresh, hot alkaline liquor is injected, and the siderably reduced wall thickness and much lower
bottom section in the area of the blow valve. maintenance costs.
Internal accessories such as scrapers and chip
screens are usually fabricated from Type 316L 2. liquor Heaters
stainless steeL Construction of digesters with clad Shell and tube heat exchangers are used to heat
Type 316L stainless steel would allow for con- the digester liquor prior to its introduction into

33
both batch and continuous digesters., Results of a Table lit
corrosion test in such a heater are shown in Table Corrosion Test in Kraft Pulping
LII. These data may indicate a lower than actual Exposed 68 Days in Head of liquor Heater
corrosion rate for carbon steel, since the heat Flow rate of 2400 gpm at temperature of 173 C (344 F).
exchanger tube walls are at a temperature higher
Corrosion Rate,
than the liquor in which the test specimens were Material mils per year
exposed. The liquor contains a large proportion of Type 304 Stainless Steel 0.5
fresh caustic and sulfide in addition to some black Type 316 Stainless Steel 0.8
liquor recovered from a previous digester cook. INCONEL alloy 600 0.9
MONEL alloy 400 38
Experience over many years has proven the ade-
Nickel 200 57
quacy of annealed Type 304 stainless steel for this Mild Steel 95
service. The use of "as-welded" tubes has some- Cast Iron 342
times resulted in failure by intergranular cor-
rosion immediately adjacent to the weld. This type Vapor domes in the hottest effects are often clad
of corrosion has not been observed when tubes with Type 804Lor Type 316L stainless steel, since
are used that have been made in compliance with carbon steel in this area may corrode at a rate
ASTM A 249. This specification caUs for welded, exceeding 100 mils per year. There are also instal-
drawn, quench-annealed tubing. Tubes of this lations where sta.inless-elad steel has been used for
type have been known to last in excess of.10 years, the entire evaporator body. Advantages of such
but service life is dependent on specific operating construction.inelude less carry..over of corrosion
conditions. In a few instances, the Type 304 stain- products and less fouling of the evaporator tubes
less steel tubes have been subject to failure by by these products.
chloride stress-corrosion crackng. Alloy 600 and Defiectorpla.tes and auxiliary piping are usu-
Alloy 20 have been successfully employed to resist any made of solid Type 804L stainless steeL For
this type of attack. valves and pumps, Ni-Resist Type 2, CF-8 and
CF-8M castings are used.
3. Black liquor Evaporators
To permit recovery of chemical values in the 4. Recausticizing
digester liquor when chip cooking is complete, it As part of the operation to regenerate chemi-
is necessary to concentrate the liquor, together cals reclaimed from the recovery furnace, sodium
with the chip wash water. This is required to raise carbonate is treated calcium hydroxide
the solids content to more than 50 per cent. which (milk of lime) to produce sodium hydroxide.
will permit burning in the recovery furnace.
Kraft liquor vacuum evaporators are multiple
Table lin
units usually consisting of one or more sets of six
long tube vertical effects connected in series. Corrosion Test in Kraft Pulping
Corrosive conditions on the tubes are somewhat Exposed 68 days in green Uquor. 175 to ~5 gpl as Na 2 CO,
in flow bQx.from recovery furnace to claSSIfiers.
less severe than in digester liquor heaters since Temperature: 66 to 99 C.(150to 210 F).
the vacuum operation results in lower boiling Some aeration and agitation.
temperatures. The first effect operates at the
Corrosion Rate,
highest temperature of about 135 C (275 F). Tem- Material mils per year
peratures decrease in each succeeding effect. It
tN(:ONEL alloy 600 <0.1
has been customary to use Type 304 stainless Type 302 Stain1ess Steel 0.1
steel for tubes in the first effect and often in the Type 309 Stainless Steel 0.1
second effect. A number of installations have used Type 310 Stainless Steel 0.1
Type 316 Stainless Steet 0.2
Type 304 stainless steel tubes in all effects, re- Nickel 200 0.3
sulting in less frequent downtime fer cleaning, MONEL alloy 400 0.5
long service Hfe, and maintenance of high heat Mild Steel 115
Cast Iron 176
transfer rates.

34
 Carbon steel, with a corrosion allowance. has
been used for most of the equipment. As shown
in Table LIII, fairly high rates can occur on car-
bon steeL Light gauge Type 304 stainless steel
is an economic selection for troublesome areas.
F. Aluminum Indu~try
Despite extensive use of caustic soda by the
aluminum illdustry for the extractioRofhydrated
alumina from bauxite in the Bayer process, rela-
Fig. 21 - This ll·foot long. 16·inch diameter pipe has been
electmplated with nickel to yield a 30-mil thick deposit on
the inner diameter and about 2 mils on the outer diameter.
Sections like this are welded toget:he( to form piping used
in bauxite refining in the aluminum industry. Lengths of
greater than 11 feet can also be plated.
Photo by courtesy of Plating Engineering Company. Milwaukee. Wise.
35
tively smallam{llwts of nickel and nickel altoys
have been utiJized in these plants.
Alloy 400 tubes have been successfully em-
ployed for digester preheaters. and Alloy 400
insert ferrules have been used to overcome the
inlet end corrosion in other steel preheater tubes.
Relatively thick (30 mils minimum) electroplated
nickel {lll steel has been used to advantage for
piping and digester preheater channels. Nickel
weld-overlays haVe proven \Iseful on pump cas-
ings, and cast nickel (ACI CZ-IOO) has given good
service as pump impellers. valve bodies and for
other instrumentation.
However. the present practice with bauxite
digesters is to use thick-walled carbon steel at
low stress levels. Some cases of stress-corrosion
cracking (If steel have occurred in plants handling
caustic soda solutions in the Bayer extraction
process. z::>
The recent trend awaYI;r;om ores high in gibbs-
ite C{lntent toward the use of Ores relatively high
in boehmite c()ntent has necessitated digester
operation at higher pressures and temperatures.
This increases the pos!;;ibHity of caustic embrittle-
ment of steeL Thus. nickel or nickel-clad steel
should be given consideration for the processing
of these higher boehmite bauxites.
G. Caustic FuSions
Nickel 200 and Nickel 201 are useful as mate-
rials of construction for vessels for the caustic
fusi{ln of·· organic comp{lunds. Where tempera-
tures exceed 316 C (600 F). the low.-carb{ln
Nickel 201 is preferred to preclude grain bound-
ary precipitation of carbon which greatly reduces
duetility. For those reactions where sulfur com-
pounds are present at temperatures over 250 to
300 C (482 to 572 F). either in the process or the
heating medium, nickel may be attacked inter-
granularly and Alloy 600 is preferred.
One process for the production of resorcinol
has involved the caustic fusion of benzene meta
disulfonic acid at 325 C (617 F). Equipment for
this production has been made of wrought Alloy
600 and ACI CY -40 castings. Both alloys should
be stress-relieved as indicated in the section on
nickel-chromium alloys (Part II B).
 H. Petroleum Refining
Cau~tic soda or, occasionally, caustic potash or
sodium carbonate is used in petroleum refining
for acid neutralization and the removal of unde-
sirables such as mercaptans and hydrogen sulfide.
Aqueous solutions may range from 2 to 50
per cent.
For many of the applications where temper-
ature and concentration are low, the corrosive
conditions are mild enough that steel can be used.
Where the corrosive conditions are more aggres-
sive, Nickel 200, AHoy 400 or Alloy 600 are used.
Very often Alloy 400 is used because it appears to
have a greater tolerance for the impurities
present in the process.
In the t'egeneration of caustic solutions, it is
common practice to use Alloy 400 in critical por-
tions of the system where steel is unsuitable.
These locations include the regenerator reboiler,
preheaters and piping for handling hot caustic
solutions and sometimes for the bottom sections
of the regenerator towers. These components may
be either solid or clad. ACI CZ-IOO, ACI M-35
ductile Ni-Resists and WORTHITE stainless steei
have been used for valves and pumps. The results
of plant corrosion tests in the reboilers of caustic
regenerator units are shown in Table LIV.
Table ltV
Plant Corrosion Tests in
Caustic Regeneration Units
Test A-In open tank used to boil 18 to 22% caustic soda
plus merca pta ns and cresolates for regeneration of
caustic solution. Test specimens were immersed in
solution above heating coils.
Test Period: 30 days.
Temperature 38 to 104 C (100 to 220 F).
Average 80 C (175 F).
Test a-Just ab~ve reboiler inlet below bottom tray of reo
generating tower. Solution 18% caustic soda for·
tified with naphthenic acid. cresols and phenols to
22 to 28 ·Be. Solution also contained 0.040/0 mer·
captan sulfur.
Test Period: 660 days.
Temperature: 21 to 116 C (70 to 240 f).
Average 107 C (225 F).
Test C-At bottom of stripping tower 18 inches above reo
boiler tubes. Solution 7 % caustic soda with trace
of mercaptans.
Test Period: 354 days.
Temperature: 121 to 149 C (250 to 300 F).
Average 135 C (275 Fl.
Test o-In vapor sectj~n of caustic soda regeneration unit.
Solution entenng contained' 13.2% caustic soda.
0.37% sulfide sulfur and 0.80% mercaptide sulfur.
Test Period: 55 days.
Temperature: 150 C (300 F).

Corrosion Rate. mils per year

Material TestA TestS Test C Test D
INCONEl alloy 600· <0.1 <0.1 <0.1 0.3
Type 304 Stainless Steel" • 0.1 0.1 0.1
Nickel 200 0.1 0.2 1.1 2.0
MONEL alloy 400 0.3 0.1 0.9 2.0
Type 316 Stainless Steel"· 0.4 0.2
Copper·Nickel alloy CA 715 1.1 4.5
Fig. 22 - Nickel·copper alloy 400 was used for the walls of Hi·Resist Type 1 3.8 4.0 13.0
the caustic stripper towers. reboiler tube bundles and hot Cast Iron 13.0 10.0
caustic lines in this refinery. After 10 years of service. the Carbon Steel·· 29 12.0 33.0
Alloy 400 components continue to withstand the corrosive
mineral acids. sulfur compounds and hot caustic soda in .., Subject to pitting.
the fluid hydroformer and caustic regenerating equipment. "') May be 'Subject to stress-corrosion cracking_

36
 In view of its good resistance to caustic alkalies
containing hydrogen sulfide and mercaptans, Al-
loy 600 is also a useful material for evaporator
tubes or other parts of regenerator systems. Alloy
600, rather than Nickel 200 or AHoy 400, should be
used in this service where metal temperatures in
excess of about 250 to 300 C (482 to 572 F) are
encountered, since Nickel 200 and Alloy 400 are
subject to sulfidation at higher temperatures.
A caustic stripper, at a major Louisiana refin-
ery, constructed of MONEL alloy 400, exhibited no
detectable metal loss after more than 4 l'2 years'
service handling up to 45<; caustic soda at tem-
peratures up to 143 to 149 C (290 to 300 F). It is
still giving repair-free service after 15 years.
In one Texas refinery, mercaptains are removed
by the Dualayer Process * which utilizes two
layers of immiscible solvents. The first solvent
layer, a water solution of caustic· potash and
potassium cresylate, removes the mercaptans.
The second and lower layer is a water solution
of caustic potash that maintains the composition
of the upper layer. Water and potassium hydrox-
ide migrate between lower and upper levels, sus-
taining the equilibrium. MONEL alloy 400 was used
for the stripper preheater, reboiler. and stripping
tower trays and. in a cast form (ACI M-35), for
the bottom pump. The tower itself was lined with
MONEL aHoy 400 and stress-relieved. This equip-
ment continues in operation after 20 years.
Nickel-copper alloy 505 has excellent non-
galling properties and can be combined with cast
nickel-copper alloy ACI M-35 in pump assemblies
to avoid seizing. particularly in mixtures contain-
ing gasoline or similar solvent materials where
lubrication is practically impossible.
L Caustic Oescaling
Several processes involving molten caustic soda
are in commercial use for the descaling of various
metals and-alloys, particularly the stainless steels.
Some of these processes involve addition to the
caustic of reducing agents to reduce the metallic
oxides to metal or lower metal oxides, most of
which flake off in the subsequent water quench.
• Patented Process. Mohil Oil Corp.
37
I n one process, the parts to be descaled are immer-
sed in a 370 C (700 F) bath of molten caustic soda
containing 1.5-2% sodium hydride. Other proc-
esses operate with molten caustic at 480 C (900
F) or higher.
Carbon steels are often used for the equipment
handling these fused caustic baths up to about
480 C (900 F). In cases where carbon steel has
not proven satisfactory. Nickel 201 and Alloy
600 have been demonstrated to give good per-
formance. Nickel 201 is used for sodium hydride
generators in one process. Both Nickel 201 and
Alloy 600 are used for sheathing on electric heat-
ing elements in caustic baths. AHoy 600 is used
for gas-fired heater tubes in some cases. In cases
where the caustic baths are operated at higher
temperatures than usual, such as 566 to 621 C
(1050 to 1150 F), Nickel 201 is used instead of
carbon steel for pickling tanks and associated
equipment. A plant corrosion test in a commercial
molten caustic pickling bath operating at 482 C
(900 F) showed a corrosion rate of one mil per
year for nickel in a 60-day test.
J. Reclaiming Caustic for Economy
and Pollution Control
In the diverse industries which make use of
caustic solutions, numerous companies have
found that it is economically attractive to reclaim
and concentrate the caustic values of their effiu-
ents. Even the return on investment for
caustic recovery units is not high enough for justi-
fication on this basis alone. pollution control is
desirable and may become mandatory as local
anti-pollution laws become more stringent.
Recovery and concentration plants are commer-
cially available for some industries. Of the total
caustic soda purchased yeariy by a textile mill
for mercerizing cotton. often as much as 65 per
cent can be recovered from the mercerizingframes
and up to 95 per cent at the mercerizer. The con-
centration of caustic soda is from about 5 per cent
in contaminated liquor to the de~;jred concentra-
tion for the particular mercerizing operation.
These plants utilize nickel or high nickel alloys for
evaporators and associated equipment .
 PART V. WELDING

A. Fabrication of Table LV
Nickel-Clad Equipment Corrosion of Iron·Contaminated Nickel Welds
in 73% Caustic Soda at 121 C (250 F) 27
In the welding of nickel-clad equipment, a cer-
tain amount of iron dilution of the nickel weld Corrosion Rate, mils per year
deposit occurs. Special precautions are usually Iron First Second Total
taken in order to minimize this dilution. With in Weld, Exposure, Exposure, Exposure,
% 30 days 60 days 90 days
special precautions, the nick~l welds in a nickel-
clad tank for a chemical tanker were limited to 0.51 8 5 6
5.56 8 5 6
an iron content of 0.35-3.29%.26 Gegner has sug- 11.43 7 5 5
gested that considerably more iron than this can 13.15 7 4 5
be tolerated. 27 17.62 7 5 5
22.85 6 4 5
Although iron-contaminated nickel weld metal
and nickel-iron alloys are not severely attacked in
Table lVI
73% caustic soda at 121 C (250 F). as shown by
data in Tables LV and LVI, nickel-iron alloys can Corrosion of Nickel and Nickel·lronAlloys
in 73% Caustic Soda at 121 C {250 f)27
be the anode in an electrolytic cell with nickel,
as shown in Table LVII. Note that the 20% iron Corrosion Rate,
alloy corroded at three to five times the rate it did Iron. % mils per year

when it was not coupled to nickel. Even greater . 0 7

increases in rate would be expected in large pieces 0 7
5 8
of equipment where the relative ratio of cathodic 5 8
area (cladding) to anodic areas (weld) is greater 10 6
than the 10:1 ratio of the test. to 8
20 8
20 8

Table LVII
Galvanic Corrosion Tests in Caustic Soda
of Nickel to Nickel-Iron Alloy Couples
Area: Nickel 0.5 sq dm Aeration: None.
Nickel·lron Alloy O.05sq dm Test Period: 7 days.
Motion: None.

Corrosion Rate. mils per year

50% HaOH at
Couple Couple 23% NaOH at 105 C (221 Fl 15C (161 Fl 15% NaOH at 126 C (259 Fl
No. Materials Coupled Uncoupled Coupled Coupled Uncoupled

5% Fe·Ni 1.6 1.4 2.4 1.0 1.0

Nickel 0.6 0.4 0.8 1.6 1.5

2 10% fe·Ni 2.6 L2 2.0 1.5 1.4

Nickel 0.4 0.4 0.6 LO 1.5

3 20% Fe·Ni 3.6 0] 1.6 1.8 0.6

Nickel 0.6 0.4 0.4 1.1 1.5
Notes:
1. The iron·nicket alloys were in the form of castings.
2. No tests were made, uncoupled. in the 500/0 NaOH solution.

38

B. Repair of Equipment in
Caustic Service
Before doing any repair or maintenance weld-
ing of nickel or nickel-containing alloys or dad-
steel plate that has been in caustic service, it is
necessary to remove products of corrosion, and
any other foreign material, from the vicinity of
the area to be welded. (The caustic soda and other
impurities present can cause loss of ductility and
cracking if present during welding.) Therefore,
great care should be taken to obtain a clean, bright
metal surface over an area extending 2 to 3 inches
from the site of welding on both sides of the piece.
Cleaning mechanicalIy, by grinding with either a
fine wheel or a disc grinder, or chemically, by
pickling, is recommended. After cleaning, the
welding procedures outlined for new metal should
be followed in every detaiL
Flash pickling solutions are effective for clean-
ing nickel and high nickel alloy surfaces. These
may be applied with long-handled swabs or
brushes where equipment is large, or may be held
in glass or ceramic crocks for pieces that are
easily handled. such as the ends of nickel caustic
evaporator tubes that have been removed from
evaporator service and are to be used for pipe-
lines. The tubes can be dipped vertically and
cleaned for a minimum distance of 3 inches from
the end.

AVAILABLE LITERATURE
The following Corrosion Engineering Bulletins are available for your use:

"Resistance of Nickel and High Nickel Alloys to Corrosion by Sulfuric

Acid"

"Corrosion Resistance of Nickel and Nickel-Containing Alloys in Caustic

Soda and Other Alkalies"
"Resistance of Nickel and High Nickel Alloys to Corrosion by Hydro-
chloric Acid, Hydrogen Chloride and Chlorine"

"Corrosion Resistance of Nickel-Containing Alloys In Phosphoric Acid"

"Corrosion Resistance of Nickel-Containing Alloys in Hydrofluoric Acid,

Hydrogen Fluoride and Fluorine"

39
 REFERENCES
1. Swandby, R. K., "Corrosion Charts: Guides to Ma-
terials Selection", Chen!. Eng., Vol. 69, No. 11, Nov.
12, 1962, p. 197.
2. Fontana, M. G., "Corrosion at Elevated Temperatures
and Pressures", The Ohio State University Research
Foundation, Report No. 10, Project 350, May 1, 1951,
p.F2.
3. Badger, W. L. and Standiford, F. C., "Anhydrous
NaOH: Today's Technology", Chern. Eng., 61, Feb.
1954, pp. 183-187.
4. Gregory, J. N., Hodge, N. and Iredale, J. V. G., "The
Static Corrosion of Nickel and Other Materials in
Molten Caustic Soda", AERE CIM 272, March, 1958.
5. Gregory, J. N., Hodge, Nand Iredale, J. V. G., "The
Corrosion and Erosion of Nickel by Molten Caustic
Soda and Sodium Uranate Suspensions Under Dy-
namic Conditions", AERE CIM 273, March, 1956.
6. Lad, R. A. and Simon, S. L., "A Study of Corrosion
and Mass Transfer of Nickel by Molten Sodium
Hydroxide", Corrosion, 10, December. 1954, pp. 435-
439.
7. Smith; G. P., Sieidlitz, M' E. and Hoffman, E. E.,
"Corrosion and Metal Transport in Fused Sodium
Hydroxide", Co)Tosion. 13, September, October, 1957.
pp. 561t-564tand 627t-630t.
8. Forestieri, A. F. and Lad, R. A., "The Use of Metallic
Inhibitors for Eliminating Mass Transfer and Corro-
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Hydroxide", Lewis Flight Propulsion Laboratory,
Cleveland, Ohio, February, 1955, NACA RM E54L13.
9. May, C. E_, "Correlation Between Hydro~en Pressure
and Protective Action of Additives in the Molten
Sodium Hydroxide-Nickel System", Lewis Flight
Propulsion Laboratory, Cleveland, Ohio, February,
1966. NACA RM E55LOl.
10. Wallace, T. and Fleck, A., "Some Properties of Fused
Sodium Hydroxide", Jourl/al Chelll. Suc., 119, 1921,
p. 1839.
11. Uhlig, H. H., Ed., Corrosion Handbook. N. Y., John
Wiley, and Sons, Inc., 1948, pp. 576-577.
12. Stone, J. M., "Solutions Causin~ Intergranular Cor-
rosion of Stainless Steels", Information from Internal
Document by courtesy of E. L du Pont de Nemours and
Co., October, 1955.
13. Agrawal, A. K. and Staehle, R. W., "Stress-Corro-
sion Cracking of Fe-Cr-Ni Alloys in Caustic Environ-
40
ments", Report No. COO-2018-21 (Q6) for period
April 15, 1970-July 14, 1970, Ohio State University,
Columbus, Ohio.
14. Nathorst, H., "Stress Corrosion Cracking of Stainless
Steels-Part I Practical Experiences", Welding Re-
search Council Bulletin, No.6, October, 1950, pp. 6-7
and 10.
15. ASM Committee on Stainless Steel in Chemical Corro-
sion Service,lHetals Handbook, Am. Soc. Metals, 1961,
p.566.
16. Beck, F. H. and Fontana, M. G., "Corrosion by
Aqueous Solutions at Elevated Temperatures and
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 TRADEMARKS

Following is a list of the registered trademarks referred to in this publication

together with the names of the trademark owners.

• • • • • • •

ALOYCO Registered trademark of Aloyco Inc.

CARPENTER Registered trademark of Carpenter Technology Corporation.

CHLORIMET Registered trademark of The Duriron Company. Inc.
DURANICKEL Registered trademark of The International Nickel Company. Inc.
DURIMET Registered trademark of The Duriron Company. Inc.
HASTELLOY Registered trademark of Cabot Corporation.
ILLIUM Registered trademark of Stainless Foundry & Engineering, Inc.
I NCOLOY Registered trademark of The International Nickel Company. Inc.
INCONEL Registered trademark of The International Nickel Company. Inc.
KAMYR Registered trademark of Kamyr Inc.
MONEL Registered trademark of The International Nickel Company. Inc.
NIMONIC Registered trademark of The International Nickel Company. Inc.
WORTHITE Registered trademark of Worthington Corp.